1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone refrigerant and heat transfer compositions comprising a fluoroether

ABSTRACT

Compositions of 1,1,1,2,2,4,5,5,5-nonafluoro-4(trifluoromethyl)-3 pentanone can be used in heat transfer refrigeration and air conditioning systems. The compositions may be in combination with fluoroethers. The compositions may be azeotropic or near azeotropic.

CROSS REFERENCE(S) TO RELATED APPLICATION(S)

This application is a divisional of U.S. application Ser. No.11/063,178, filed Feb. 22, 2005, now U.S. Pat. No. 7,252,780 whichclaims the priority benefit of U.S. Provisional Application 60/575,037,filed May 26, 2004, and U.S. Provisional Application 60/584,785, filedJun. 29, 2004, each of which is incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to compositions for use in heat transferrefrigeration and air conditioning systems comprising1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and atleast one fluoroether including refrigeration and air-conditioningsystems employing a centrifugal compressor. The compositions of thepresent invention may be azeotropic or near azeotropic.

2. Description of Related Art

The refrigeration industry has been working for the past few decades tofind replacement refrigerants for the ozone depletingchlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) beingphased out as a result of the Montreal Protocol. The solution for mostrefrigerant producers has been the commercialization ofhydrofluorocarbon (HFC) refrigerants. The new HFC refrigerants, HFC-134abeing the most widely used at this time, have zero ozone depletionpotential and thus are not affected by the current regulatory phase outas a result of the Montreal Protocol.

Further, environmental regulations may ultimately cause global phase outof certain HFC refrigerants. Currently, the automobile industry isfacing regulations relating to global warming potential for refrigerantsused in mobile air-conditioning. Therefore, there is a great currentneed to identify new refrigerants with reduced global warming potentialfor the automobile air-conditioning market. Should the regulations bemore broadly applied in the future, an even greater need will be feltfor refrigerants that can be used in all areas of the refrigeration andair-conditioning industry.

Currently proposed replacement refrigerants for HFC-134a includeHFC-152a, pure hydrocarbons such as butane or propane, or “natural”refrigerants such as CO₂ or ammonia. Many of these suggestedreplacements are toxic, flammable, and/or have low energy efficiency.Therefore, new alternatives are constantly being sought.

The present invention provides compositions, including refrigerantcompositions and heat transfer fluids, that provide characteristics tomeet the demands of low or zero ozone depletion potential and lowerglobal warming potential.

BRIEF SUMMARY OF THE INVENTION

The present invention relates to compositions, including refrigerant orheat transfer fluid compositions selected from the group consisting of:

-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-(difluoromethoxy)-1,1,2-trifluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-(difluoromethoxy)-1,2,2-trifluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2-fluoromethoxy-1,1,1,2-tetrafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-methoxy-1,1,2,2-tetrafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2-methoxy-1,1,1,2-tetrafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-difluoromethoxy-2,2-difluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2-methoxy-1,1,2-trifluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1-difluoro-2-methoxyethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,2,2-tetrafluoro-3-(trifluoromethoxy)propane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-(2,2-difluoroethoxy)-1,1,2,2,2-pentafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,3,3,3-hexafluoro-2-(trifluoromethoxy)propane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,2-trifluoro-1-methoxy-2-(trifluoromethoxy)ethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,2,3,3-hexafluoro-3-methoxypropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,3,3,3-hexafluoro-2-methoxypropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,2,2,3,3-hexafluoro-3-methoxypropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-(1,1,-difluoroethoxy)-1,1,2,2-tetrafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    3-(difluoromethoxy)-1,1,2,2-tetrafluoropropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,2,2-pentafluoro-3-methoxypropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2-(difluoromethoxy)-1,1,1-trifluoropropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2-ethoxy-1,1,1,2-tetrafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1-trifluoro-2-ethoxyethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1-trifluoro-3-methoxypropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1-trifluoro-2-methoxypropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-ethoxy-1,2,2-trifluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,2,3,3-hexafluoro-3-(pentafluoroethoxy)propane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2-ethoxy-1,1,1,2,3,3,3-heptafluoropropane:-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    3-ethoxy-1,1,1,2,2,3,3-heptafluoropropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-(1,1,2,2-tetrafluoroethoxy)propane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-ethoxy-1,1,2,2-tetrafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2,3-difluoro-4-(trifluoromethyl)oxetane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    C₄F₉OCH₃;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    C₄F₉OC₂H₅; and-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,2,2,3,3-heptafluoro-3-methoxypropane.

The above listed compounds may be used in refrigeration, heat transferor air conditioning systems employing a centrifugal compressor, atwo-stage centrifugal compressor and/or a single slab/single pass heatexchanger.

The present invention also relates to processes for producingrefrigeration, heat, and transfer of heat from a heat source to a heatsink using the present inventive compositions.

DETAILED DESCRIPTION OF THE INVENTION

Applicants specifically incorporate the entire contents of all citedreferences in this disclosure. Further, when an amount, concentration,or other value or parameter is given as either a range, preferred range,or a list of upper preferable values and lower preferable values, thisis to be understood as specifically disclosing all ranges formed fromany pair of upper range limit or preferred value and any lower rangelimit or preferred value, regardless of whether such ranges areseparately disclosed. Where a range of numerical values is recitedherein, unless otherwise stated, the range is intended to include theendpoints thereof, and all integers and fractions within the range. Itis not intended that the scope of the present invention be limited tothe specific values recited when defining a range.

The compositions of the present invention comprise1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone (PEIK) andat least one fluoroether.

The fluoroethers of the present invention comprise compounds containinghydrogen, fluorine, carbon and at least one ether group oxygen. Thefluoroethers may be represented by the formula R¹OR², wherein R¹ and R²are independently selected from straight or branched chain aliphaticfluorinated hydrocarbon radicals. R¹ and R² may be joined to form acyclic fluoroether ring. The fluoroethers may contain from about 2 to 8carbon atoms. Preferred fluoroethers have from 3 to 6 carbon atoms.Representative fluoroethers are listed in Table 1. Representativecompounds that may be components of the compositions of the presentinvention are listed in Table 1.

TABLE 1 CAS Reg. Compound Chemical Formula Chemical Name No.Fluoroethers HFOC-236caE CHF₂OCF₂CHF₂ 1-difluoromethoxy-1,1,2,2-32778-11-3 tetrafluoroethane HFOC-236eaEβγ CHF₂OCHFCF₃2-difluoromethoxy-1,1,1,2- 57041-67-5 tetrafluoroethane HFOC-245caEαβCHF₂OCF₂CH₂F 1-(difluoromethoxy)-1,1,2- 69948-24-9 trifluoroethaneHFOC-245cbEβγ CF₃CF₂OCH₃ 1,1,1,2,2-pentafluoro-2-methoxyethane22410-44-2 HFOC-245eaE CHF₂OCHFCHF₂ 1-(difluoromethoxy)-1,2,2-60113-74-8 trifluoroethane HFOC-245ebEβγ CF₃CHFOCH₂F2-fluoromethoxy-1,1,1,2- 56885-27-9 tetrafluoroethane HFOC-245faEαβCHF₂CH₂OCF₃ 1,1-difluoro-2-trifluoromethoxyethane 84011-15-4HFOC-245faEβγ CF₃CH₂OCHF₂ 2-difluoromethoxy-1,1,1-trifluoroethane1885-48-9 HFOC-254cbEβγ CHF₂CF₂OCH₃ 1-methoxy-1,1,2,2-tetrafluoroethane425-88-7 HFOC-254ebEβγ CF₃CHFOCH₃ 2-methoxy-1,1,1,2-tetrafluoroethane148380-63-6 HFOC-254faE CHF₂OCH₂CHF₂1-difluoromethoxy-2,2-difluoroethane 32778-16-8 HFOC-263ebEβγCH₃OCHFCHF₂ 2-methoxy-1,1,2-trifluoroethane 56281-91-5 HFOC-263fbEβγCF₃CH₂OCH₃ 2-methoxy-1,1,1-trifluoroethane 460-43-5 HFOC-272fbEβγCH₃OCH₂CHF₂ 1,1-difluoro-2-methoxyethane 461-57-4 HFOC-338mcfEβγCF₃CF₂OCH₂CF₃ 1,1,1,2,2-pentafluoro-2-(2,2,2- 156053-88-2trifluoroethoxy)ethane HFOC- CF₃CHFOCHFCF₃1,1′-oxybis(1,2,2,2-tetrafluoro)ethane 67429-44-1 338meeEβγ HFOC-(CF₃)₂CHOCHF₂ 2-(difluoromethoxy)-1,1,1,3,3,3- 26103-08-2 338mmzEβγhexafluoropropane HFOC-338peEγδ CHF₂OCHFCF₂CF₃3-(difluoromethoxy)-1,1,1,2,2,3- 60598-11-0 hexafluoropropane HFOC-CF₃CF₂CF₂OCH₃ 1,1,1,2,2,3,3-heptafluoro-3- 375-03-1 347mccEγδmethoxypropane HFOC-347mcfEβγ CHF₂CH₂OCF₂CF₃1-(2,2-difluoroethoxy)-1,1,2,2,2- 171182-95-9 pentafluoroethaneHFOC-347mcfEγδ CHF₂OCH₂CF₂CF₃ 3-(difluoromethoxy)-1,1,1,2,2- 56860-81-2pentafluoropropane HFOC- CF₃OCH₂CF₂CHF₂ 1,1,2,2-tetrafluoro-3- 1683-81-4347mfcEαβ (trifluoromethoxy)propane HFOC- CH₂FOCH(CF3)₂1,1,1,3,3,3-hexafluoro-2- 28523-86-6 347mmzEβγ (fluoromethoxy)propaneHFOC-347pcfEβγ CF₃CH₂OCF₂CHF₂ 1-(2,2,2-trifluoroethoxy)-1,1,2,2-406-78-0 tetrafluoroethane HFOC- CH₃OCF₂CHFOCF₃1,1,2-trifluoro-1-methoxy-2- 996-56-5 356mecE2αβγδ(trifluoromethoxy)ethane HFOC- CH₃OCF₂CHFCF₃ 1,1,1,2,3,3-hexafluoro-3-382-34-3 356mecEγδ methoxypropane HFOC- (CF₃)₂CHOCH₃1,1,1,3,3,3-hexafluoro-2- 13171-18-1 356mmzEβγ methoxypropaneHFOC-356pccEγδ CHF₂CF₂CF₂OCH₃ 1,1,2,2,3,3-hexafluoro-3- 160620-20-2methoxypropane HFOC-356pcfEβγ CHF₂CF₂OCH₂CHF₂1-(1,1-difluoroethoxy)-1,1,2,2- 50807-77-7 tetrafluoroethaneHFOC-356pcfEγδ CHF₂OCH₂CF₂CHF₂ 3-(difluoromethoxy)-1,1,2,2- 35042-99-0tetrafluoropropane HFOC- CHF₂OCH(CH₃)(CF₃) 2-(difluoromethoxy)-1,1,1-327893-56-9 365mpzEβγ trifluoropropane HFOC-365mcEγδ CF₃CF₂CH₂OCH₃1,1,1,2,2-pentafluoro-3- 378-16-5 methoxypropane HFOC-374mefEβγCF₃CHFOCH₂CH₃ 2-ethoxy-1,1,1,2-tetrafluoroethane 50285-06-8HFOC-374pcEβγ CH₃CH₂OCF₂CHF₂ 1-ethoxy-1,1,2,2-tetrafluoroethane 512-51-6HFOC-383mEαβ CF₃OCH₂CH₂CH₃ 1-(trifluoromethoxy)propane 59426-77-6HFOC-383mEβγ CH₃CH₂OCH₂CF₃ 1,1,1-trifluoro-2-ethoxyethane 461-24-5HFOC-383mEγδ CF₃CH₂CH₂OCH₃ 1,1,1-trifluoro-3-methoxypropane 461-22-3HFOC-383mzEβγ CH₃OCH(CH₃)(CF₃) 1,1,1-trifluoro-2-methoxypropane32793-45-6 HFOC-383peEβγ CHF₂CHFOCH₂CH₃ 1-ethoxy-1,2,2-trifluoroethane20202-98-6 HFOC-42- CF₃CF₂CF₂OCHFCF₃1,1,1,2,2,3,3-heptafluoro-3-(1,2,2,2- 3330-15-2 11meEγδtetrafluoroethoxy)propane HFOC- CF₃CHFCF₂OCF₂CF₃1,1,1,2,3,3-hexafluoro-3- 142469-07-6 42-11meEβγ(pentafluoroethoxy)propane HFOC- CH₃CH₂OCF(CF₃)₂ 2-ethoxy-1,1,1,2,3,3,3-22137-14-0 467mmyEβγ heptafluoropropane HFOC- CH₃CH₂OCF₂CF₂CF₃3-ethoxy-1,1,1,2,2,3,3- 22052-86-4 467mccEγδ heptafluoropropane HFOC-CH₃CH₂OCH(CF₃)₂ 2-ethoxy-1,1,1,3,3,3-hexafluoropropane 18339-53-8476mmzEβγ HFOC-494pcEβγ CH₃CH₂CH₂OCF₂CHF₂1-(1,1,2,2-tetrafluoroethoxy)propane 380-48-3 HFOC-494pcEγδCH₃CH₂OCH₂CF₂CHF₂ 3-ethoxy-1,1,2,2-tetrafluoropropane 24566-96-9HFOC-494pczEβγ (CH₃)₂CHOCF₂CHF₂ 2-(1,1,2,2-tetrafluoroethoxy)propane757-11-9 HFOC- c-OCF₂CHFCHFCF₂— 2,2,3,4,5,5-hexafluorotetrahydrofuran24280-80-6 C336ceeEαβ HFOC- c-OCHFCHFCH(CF₃)—2,3-difluoro-4-(trifluoromethyl)oxetane 74985-21-0 C345mzeEαβ C₄F₉OCH₃CF₃CF₂CF₂CF₂OCH₃ 1,1,1,2,2,3,3,4,4-nonafluoro-4- 163702-07-6 (mixture ofmethoxybutane isomers) (CF₃)₂CFCF₂OCH₃ 2-(methoxydifluoromethyl)-163702-08-7 1,1,1,2,3,3,3-heptafluoropropane C₄F₉OC₂H₅ CF₃CF₂CF₂CF₂OC₂H₅1-ethoxy-1,1,2,2,3,3,4,4,4- 163702-05-4 (mixture of nonafluorobutaneisomers) (CF₃)₂CFCF₂OC₂H₅ 2-(ethoxydifluoromethyl)-1,1,1,2,3,3,3-163702-06-5 heptafluoropropane Fluoroketones PEIK CF₃CF₂C(O)CF(CF₃)₂1,1,1,2,2,4,5,5,5-nonafluoro-4- 756-13-8 (trifluoromethyl)-3-pentanone(or perfluoroethylisopropyl ketone)

The compounds listed in Table 1 are available commercially or may beprepared by processes known in the prior art. C₄F₉OCH₃ and C₄F₉OC₂H₅ areboth mixtures of isomers as indicated in Table 1 and are availablecommercially from 3M™ (St. Paul, Minn.).1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone (PEIK) isalso commercially available from 3M™ (St. Paul, Minn.).

Compositions of the present invention have low or zero ozone depletionpotential and low global warming potential. For example, fluoroethersand PEIK, alone or in mixtures will have global warming potentials lowerthan many HFC refrigerants currently in use.

The compositions of the present invention may be prepared by anyconvenient method to combine the desired amounts of the individualcomponents. A preferred method is to weigh the desired component amountsand thereafter combine the components in an appropriate vessel.Agitation may be used, if desired.

The refrigerant or heat transfer compositions of the present inventioncomprise PEIK with at least one fluoroether selected from the groupconsisting of:

-   1-(difluoromethoxy)-1,1,2-trifluoroethane;-   1-(difluoromethoxy)-1,2,2-trifluoroethane;-   2-fluoromethoxy-1,1,1,2-tetrafluoroethane;-   1-methoxy-1,1,2,2-tetrafluoroethane;-   2-methoxy-1,1,1,2-tetrafluoroethane;-   1-difluoromethoxy-2,2-difluoroethane;-   2-methoxy-1,1,2-trifluoroethane;-   1,1-difluoro-2-methoxyethane;-   1,1,2,2-tetrafluoro-3-(trifluoromethoxy)propane;-   1-(2,2-difluoroethoxy)-1,1,2,2,2-pentafluoroethane;-   3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane;-   1,1,1,3,3,3-hexafluoro-2-(trifluoromethoxy)propane;-   1,1,2-trifluoro-1-methoxy-2-(trifluoromethoxy)ethane;-   1,1,1,2,3,3-hexafluoro-3-methoxypropane;-   1,1,1,3,3,3-hexafluoro-2-methoxypropane;-   1,1,2,2,3,3-hexafluoro-3-methoxypropane;-   1-(1,1,-difluoroethoxy)-1,1,2,2-tetrafluoroethane;-   3-(difluoromethoxy)-1,1,2,2-tetrafluoropropane;-   1,1,1,2,2-pentafluoro-3-methoxypropane;-   2-(difluoromethoxy)-1,1,1-trifluoropropane;-   2-ethoxy-1,1,1,2-tetrafluoroethane;-   1,1,1-trifluoro-2-ethoxyethane;-   1,1,1-trifluoro-3-methoxypropane;-   1,1,1-trifluoro-2-methoxypropane;-   1-ethoxy-1,2,2-trifluoroethane;-   1,1,1,2,3,3-hexafluoro-3-(pentafluoroethoxy)propane;-   2-ethoxy-1,1,1,2,3,3,3-heptafluoropropane:-   3-ethoxy-1,1,1,2,2,3,3-heptafluoropropane;-   1-(1,1,2,2-tetrafluoroethoxy)propane;-   2,3-difluoro-4-(trifluoromethyl)oxetane;-   C₄F₉OCH₃;-   C₄F₉OC₂H₅;-   1,1,1,2,2,3,3-heptafluoro-3-methoxypropane;-   1-ethoxy-1,1,2,2-tetrafluoroethane; and.    combinations thereof

The refrigerant or heat transfer compositions of the present inventionmay be azeotropic or near azeotropic compositions. By azeotropiccomposition is meant a constant-boiling mixture of two or moresubstances that behave as a single substance. One way to characterize anazeotropic composition is that the vapor produced by partial evaporationor distillation of the liquid has the same composition as the liquidfrom which it is evaporated or distilled, i.e., the mixturedistils/refluxes without compositional change. Constant-boilingcompositions are characterized as azeotropic because they exhibit eithera maximum or minimum boiling point, as compared with that of thenon-azeotropic mixture of the same compounds. An azeotropic compositionwill not fractionate within the refrigeration or air conditioning systemduring operation, which may reduce efficiency of the system.Additionally, an azeotropic composition will not fractionate uponleakage from the refrigeration or air conditioning system. In thesituation where one component of a mixture is flammable, fractionationduring leakage could lead to a flammable composition either within thesystem or outside of the system.

A near azeotropic composition (also commonly referred to as an“azeotropic-like composition”) is a substantially constant boiling,liquid admixture of two or more substances that behaves essentially as asingle substance. One way to characterize a near azeotropic compositionis that the vapor produced by partial evaporation or distillation of theliquid has substantially the same composition as the liquid from whichit was evaporated or distilled, that is, the admixture distills/refluxeswithout substantial composition change. Another way to characterize anear azeotropic composition is that the bubble point vapor pressure andthe dew point vapor pressure of the composition at a particulartemperature are substantially the same. Herein, a composition is nearazeotropic if, after 50 weight percent of the composition is removed,such as by evaporation or boiling off, the difference in vapor pressurebetween the original composition and the composition remaining after 50weight percent of the original composition has been removed is less thanabout 10 percent.

The azeotropic compositions, including refrigerant compositions and heattransfer fluids, of the present invention are listed in Table 2.

TABLE 2 Azeotrope Concentration Azeotrope Component A Component B Wt % AWt % B BP (° C.) PEIK HFOC-245caEαβ 47.6 52.4 34.7 PEIK HFOC-245eaE 66.233.8 40.5 PEIK HFOC-245ebEβγ 52.4 47.6 36.2 PEIK HFOC-254cbEβγ 59.7 40.327.4 PEIK HFOC-254ebEβγ 63.6 36.4 29.9 PEIK HFOC-254faE 73.3 26.7 35.9PEIK HFOC-263ebEβγ 79.4 20.6 34.4 PEIK HFOC-272fbEβγ 75.3 24.7 31.5 PEIKHFOC-347mccEγδ 39.5 60.5 32.1 PEIK HFOC-347mfcEαβ 58.8 41.2 38.6 PEIKHFOC-347mcfEβγ 57.8 42.2 38.2 PEIK HFOC-347mcfEγδ 58.5 41.5 38.4 PEIKHFOC-347mmzEβγ 78.0 22.0 44.8 PEIK HFOC- 78.6 21.4 47.6 356mecE2αβγδPEIK HFOC-356mecEγδ 73.7 26.3 38.8 PEIK HFOC-356mmzEβγ 71.0 29.0 40.8PEIK HFOC-356pccEγδ 80.6 19.4 42.9 PEIK HFOC-356pcfEβγ 86.5 13.5 45.8PEIK HFOC-356pcfEγδ 83.4 16.6 45.8 PEIK HFOC-365mcEγδ 69.0 31.0 38.5PEIK HFOC-365mpzEβγ 70.3 29.7 43.0 PEIK HFOC-374mefEβγ 79.6 20.4 41.0PEIK HFOC-374pcEβγ 74.8 25.2 39.9 PEIK HFOC-383mEβγ 73.4 26.6 39.2 PEIKHFOC-383mEγδ 78.3 21.7 39.0 PEIK HFOC-383mzEβγ 72.4 27.6 36.0 PEIKHFOC-383peEβγ 76.0 24.0 34.5 PEIK HFOC-467mmyEβγ 58.0 42.0 40.7 PEIKHFOC-467mccEγδ 68.9 31.1 43.4 PEIK HFOC-494pcEβγ 85.3 14.7 44.8 PEIKHFOC-C345mzeEαδ 78.8 21.2 41.3 PEIK C₄F₉OCH₃ 77.0 23.0 45.2 PEIKC₄F₉OC₂H₅ 96.6 3.4 48.9

The near azeotropic refrigerant compositions and heat transfer fluidsand concentration ranges of the present invention are listed in Table 3.

TABLE 3 Near Azeotropic Concentration Range Compounds (A/B) wt % A/wt %B PEIK/HFOC-245caEαβ  1-79/99-21 PEIK/HFOC-245eaE 38-99/62-1 PEIK/HFOC-245ebEβγ 20-82/80-18 PEIK/HFOC-254cbEβγ 36-82/64-18PEIK/HFOC-254ebEβγ 28-85/72-15 PEIK/HFOC-254faE 49-87/51-13PEIK/HFOC-263ebEβγ 58-91/42-9  PEIK/HFOC-272fbEβγ 53-89/47-11PEIK/HFOC-347mfcEαβ  1-85/99-15 PEIK/HFOC-347mcfEβγ  1-84/99-16PEIK/HFOC-347mcfEγδ  1-85/99-15 PEIK/HFOC-347mmzEβγ 39-99/61-1 PEIK/HFOC-356mecE2αβγδ 1-99/99-1 PEIK/HFOC-356mecEγδ 47-88/53-12PEIK/HFOC-356mmzEβγ 32-90/68-10 PEIK/HFOC-356pccEγδ 57-94/43-6 PEIK/HFOC-356pcfEβγ 60-99/40-1  PEIK/HFOC-356pcfEγδ 56-99/44-1 PEIK/HFOC-365mcEγδ 28-88/72-12 PEIK/HFOC-365mpzEβγ 1-99/99-1PEIK/HFOC-374mefEβγ 55-92/45-8  PEIK/HFOC-383mEβγ 41-91/59-9 PEIK/HFOC-383mEγδ 55-91/45-9  PEIK/HFOC-383mzEβγ 45-88/55-12PEIK/HFOC-383peEβγ 54-89/46-11 PEIK/HFOC-42-11meEβγ 1-99/99-1PEIK/HFOC-467mmyEβγ 1-99/99-1 PEIK/HFOC-467mccEγδ 1-99/99-1PEIK/HFOC-494pcEβγ 62-99/38-1  PEIK/HFOC-c345mzeEαδ 54-92/46-8 PEIK/C₄F₉OCH₃ 40-99/60-1  PEIK/C₄F₉OC₂H₅ 63-99/37-1  PEIK/HFOC-347mccEγδ 1-76/99-24 PEIK/HFOC-374pcEβγ 50-90/50-10

Additional compounds from the list in Table 1 may be added to the binarycompositions of the present invention to form ternary or higher ordercompositions.

The compositions of the present invention may further comprise about0.01 weight percent to about 5 weight percent of an additive such as,for example, a stabilizer, free radical scavenger and/or antioxidant.Such additives include but are not limited to, nitromethane, hinderedphenols, hydroxylamines, thiols, phosphites, or lactones. Singleadditives or combinations may be used.

The compositions of the present invention may further comprise about0.01 weight percent to about 5 weight percent of a water scavenger(drying compound). Such water scavengers may comprise ortho esters suchas trimethyl-, triethyl-, or tripropylortho formate.

The compositions of the present invention may further comprise anultra-violet (UV) dye and optionally a solubilizing agent. The UV dye isa useful component for detecting leaks of the refrigerant composition orheat transfer fluids by permitting one to observe the fluorescence ofthe dye in the refrigerant or heat transfer fluid composition at a leakpoint or in the vicinity of refrigeration or air-conditioning apparatus.One may observe the fluorosence of the dye under an ultra-violet light.Solubilizing agents may be needed due to poor solubility of such UV dyesin some refrigerants and heat transfer fluids.

By “ultra-violet” dye is meant a UV fluorescent composition that absorbslight in the ultra-violet or “near” ultra-violet region of theelectromagnetic spectrum. The fluorescence produced by the UVfluorescent dye under illumination by a UV light that emits radiationwith wavelength anywhere from 10 nanometer to 750 nanometer may bedetected. Therefore, if refrigerant or heat transfer fluid containingsuch a UV fluorescent dye is leaking from a given point in arefrigeration or air conditioning apparatus, the fluorescence can bedetected at the leak point. Such UV fluorescent dyes include but are notlimited to naphthalimides, perylenes, coumarins, anthracenes,phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes,fluoresceins, and derivatives or combinations thereof. Solubilizingagents of the present invention comprise at least one compound selectedfrom the group consisting of hydrocarbons, hydrocarbon ethers,polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons,esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes.

Hydrocarbon solubilizing agents of the present invention comprisehydrocarbons including straight chained, branched chain or cyclicalkanes or alkenes containing 5 or fewer carbon atoms and only hydrogenwith no other functional groups. Representative hydrocarbon solubilizingagents comprise propane, propylene, cyclopropane, n-butane, isobutane,and n-pentane. It should be noted that if the refrigerant or heattransfer fluid is a hydrocarbon, then the solubilizing agent may not bethe same hydrocarbon.

Hydrocarbon ether solubilizing agents of the present invention compriseethers containing only carbon, hydrogen and oxygen, such as dimethylether (DME).

Polyoxyalkylene glycol ether solubilizing agents of the presentinvention are represented by the formula R¹[(OR²)_(x)OR³]_(y), wherein:x is an integer from 1-3; y is an integer from 1-4; R¹ is selected fromhydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atomsand y bonding sites; R² is selected from aliphatic hydrocarbyleneradicals having from 2 to 4 carbon atoms; R³ is selected from hydrogenand aliphatic and alicyclic hydrocarbon radicals having from 1 to 6carbon atoms; at least one of R¹ and R³ is said hydrocarbon radical; andwherein said polyoxyalkylene glycol ethers have a molecular weight offrom about 100 to about 300 atomic mass units. As used herein, bondingsites mean radical sites available to form covalent bonds with otherradicals. Hydrocarbylene radicals mean divalent hydrocarbon radicals. Inthe present invention, preferred polyoxyalkylene glycol ethersolubilizing agents are represented by R¹[(OR²)_(x)OR³]_(y): x ispreferably 1-2; y is preferably 1; R¹ and R³ are preferablyindependently selected from hydrogen and aliphatic hydrocarbon radicalshaving 1 to 4 carbon atoms; R² is preferably selected from aliphatichydrocarbylene radicals having from 2 or 3 carbon atoms, most preferably3 carbon atoms; the polyoxyalkylene glycol ether molecular weight ispreferably from about 100 to about 250 atomic mass units, mostpreferably from about 125 to about 250 atomic mass units. The R¹ and R³hydrocarbon radicals having 1 to 6 carbon atoms may be linear, branchedor cyclic. Representative R¹ and R³ hydrocarbon radicals include methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, and cyclohexyl.Where free hydroxyl radicals on the present polyoxyalkylene glycol ethersolubilizing agents may be incompatible with certain compressionrefrigeration apparatus materials of construction (e.g. Mylar®), R¹ andR³ are preferably aliphatic hydrocarbon radicals having 1 to 4 carbonatoms, most preferably 1 carbon atom. The R² aliphatic hydrocarbyleneradicals having from 2 to 4 carbon atoms form repeating oxyalkyleneradicals—(OR²)_(x)—that include oxyethylene radicals, oxypropyleneradicals, and oxybutylene radicals. The oxyalkylene radical comprisingR² in one polyoxyalkylene glycol ether solubilizing agent molecule maybe the same, or one molecule may contain different R² oxyalkylenegroups. The present polyoxyalkylene glycol ether solubilizing agentspreferably comprise at least one oxypropylene radical. Where R¹ is analiphatic or alicyclic hydrocarbon radical having 1 to 6 carbon atomsand y bonding sites, the radical may be linear, branched or cyclic.Representative R¹ aliphatic hydrocarbon radicals having two bondingsites include, for example, an ethylene radical, a propylene radical, abutylene radical, a pentylene radical, a hexylene radical, acyclopentylene radical and a cyclohexylene radical. Representative R¹aliphatic hydrocarbon radicals having three or four bonding sitesinclude residues derived from polyalcohols, such as trimethylolpropane,glycerin, pentaerythritol, 1,2,3-trihydroxycyclohexane and1,3,5-trihydroxycyclohexane, by removing their hydroxyl radicals.

Representative polyoxyalkylene glycol ether solubilizing agents includebut are not limited to: CH₃OCH₂CH(CH₃)O(H or CH₃) (propylene glycolmethyl (or dimethyl)ether), CH₃O[CH₂CH(CH₃)O]₂(H or CH₃) (dipropyleneglycol methyl (or dimethyl)ether), CH₃O[CH₂CH(CH₃)O]₃(H or CH₃)(tripropylene glycol methyl (or dimethyl)ether), C₂H₅OCH₂CH(CH₃)O(H orC₂H₅) (propylene glycol ethyl (or diethyl)ether), C₂H₅O[CH₂CH(CH₃)O]₂(Hor C₂H₅) (dipropylene glycol ethyl (or diethyl)ether),C₂H₅O[CH₂CH(CH₃)O]₃(H or C₂H₅) (tripropylene glycol ethyl (ordiethyl)ether), C₃H₇OCH₂CH(CH₃)O(H or C₃H₇) (propylene glycol n-propyl(or di-n-propyl)ether), C₃H₇O[CH₂CH(CH₃)O]₂(H or C₃H₇) (dipropyleneglycol n-propyl (or di-n-propyl)ether), C₃H₇O[CH₂CH(CH₃)O]₃(H or C₃H₇)(tripropylene glycol n-propyl (or di-n-propyl)ether), C₄H₉OCH₂CH(CH₃)OH(propylene glycol n-butyl ether), C₄H₉O[CH₂CH(CH₃)O]₂(H or C₄H₉)(dipropylene glycol n-butyl (or di-n-butyl)ether), C₄H₉O[CH₂CH(CH₃)O]₃(Hor C₄H₉) (tripropylene glycol n-butyl (or di-n-butyl)ether),(CH₃)₃COCH₂CH(CH₃)OH (propylene glycol t-butyl ether),(CH₃)₃CO[CH₂CH(CH₃)O]₂(H or (CH₃)₃) (dipropylene glycol t-butyl (ordi-t-butyl)ether), (CH₃)₃CO[CH₂CH(CH₃)O]₃(H or (CH₃)₃) (tripropyleneglycol t-butyl (or di-t-butyl)ether), C₅H₁₁OCH₂CH(CH₃)OH (propyleneglycol n-pentyl ether), C₄H₉OCH₂CH(C₂H₅)OH (butylene glycol n-butylether), C₄H₉O[CH₂CH(C₂H₅)O]₂H (dibutylene glycol n-butyl ether),trimethylolpropane tri-n-butyl ether (C₂H₅C(CH₂O(CH₂)₃CH₃)₃) andtrimethylolpropane di-n-butyl ether (C₂H₅C(CH₂OC(CH₂)₃CH₃)₂CH₂OH).

Amide solubilizing agents of the present invention comprise thoserepresented by the formulae R¹C(O)NR²R³ and cyclo-[R⁴C(O)N(R⁵)], whereinR¹, R², R³ and R⁵ are independently selected from aliphatic andalicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; R⁴ isselected from aliphatic hydrocarbylene radicals having from 3 to 12carbon atoms; and wherein said amides have a molecular weight of fromabout 100 to about 300 atomic mass units. The molecular weight of saidamides is preferably from about 160 to about 250 atomic mass units. R¹,R², R³ and R⁵ may optionally include substituted hydrocarbon radicals,that is, radicals containing non-hydrocarbon substituents selected fromhalogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R¹,R², R³ and R⁵ may optionally include heteroatom-substituted hydrocarbonradicals, that is, radicals, which contain the atoms nitrogen (aza-),oxygen (oxa-) or sulfur (thia-) in a radical chain otherwise composed ofcarbon atoms. In general, no more than three non-hydrocarbonsubstituents and heteroatoms, and preferably no more than one, will bepresent for each 10 carbon atoms in R¹⁻³, and the presence of any suchnon-hydrocarbon substituents and heteroatoms must be considered inapplying the aforementioned molecular weight limitations. Preferredamide solubilizing agents consist of carbon, hydrogen, nitrogen andoxygen. Representative R¹, R², R³ and R⁵ aliphatic and alicyclichydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl,isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl,tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl and their configurational isomers. A preferredembodiment of amide solubilizing agents are those wherein R⁴ in theaforementioned formula cyclo-[R⁴C(O)N(R⁵)—] may be represented by thehydrocarbylene radical (CR⁶R⁷)_(n), in other words, the formula:cyclo-[(CR⁶R⁷)_(n)C(O)N(R⁵)—] wherein: the previously-stated values formolecular weight apply; n is an integer from 3 to 5; R⁵ is a saturatedhydrocarbon radical containing 1 to 12 carbon atoms; R⁶ and R⁷ areindependently selected (for each n) by the rules previously offereddefining R¹⁻³. In the lactams represented by the formula:cyclo-[(CR⁶R⁷)_(n)C(O)N(R⁵)—], all R⁶ and R⁷ are preferably hydrogen, orcontain a single saturated hydrocarbon radical among the n methyleneunits, and R⁵ is a saturated hydrocarbon radical containing 3 to 12carbon atoms. For example, 1-(saturated hydrocarbonradical)-5-methylpyrrolidin-2-ones.

Representative amide solubilizing agents include but are not limited to:1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one,1-octyl-5-methylpyrrolidin-2-one, 1-butylcaprolactam,1-cyclohexylpyrrolidin-2-one, 1-butyl-5-methylpiperid-2-one,1-pentyl-5-methylpiperid-2-one, 1-hexylcaprolactam,1-hexyl-5-methylpyrrolidin-2-one, 5-methyl-1-pentylpiperid-2-one,1,3-dimethylpiperid-2-one, 1-methylcaprolactam,1-butyl-pyrrolidin-2-one, 1,5-dimethylpiperid-2-one,1-decyl-5-methylpyrrolidin-2-one, 1-dodecylpyrrolid-2-one,N,N-dibutylformamide and N,N-diisopropylacetamide.

Ketone solubilizing agents of the present invention comprise ketonesrepresented by the formula R¹C(O)R², wherein R¹ and R² are independentlyselected from aliphatic, alicyclic and aryl hydrocarbon radicals havingfrom 1 to 12 carbon atoms, and wherein said ketones have a molecularweight of from about 70 to about 300 atomic mass units. R¹ and R² insaid ketones are preferably independently selected from aliphatic andalicyclic hydrocarbon radicals having 1 to 9 carbon atoms. The molecularweight of said ketones is preferably from about 100 to 200 atomic massunits. R¹ and R² may together form a hydrocarbylene radical connectedand forming a five, six, or seven-membered ring cyclic ketone, forexample, cyclopentanone, cyclohexanone, and cycloheptanone. R¹ and R²may optionally include substituted hydrocarbon radicals, that is,radicals containing non-hydrocarbon substituents selected from halogens(e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R¹ and R² mayoptionally include heteroatom-substituted hydrocarbon radicals, that is,radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-)or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.In general, no more than three non-hydrocarbon substituents andheteroatoms, and preferably no more than one, will be present for each10 carbon atoms in R¹ and R², and the presence of any suchnon-hydrocarbon substituents and heteroatoms must be considered inapplying the aforementioned molecular weight limitations. RepresentativeR¹ and R² aliphatic, alicyclic and aryl hydrocarbon radicals in thegeneral formula R¹C(O)R² include methyl, ethyl, propyl, isopropyl,butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl,tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl and their configurational isomers, as well as phenyl,benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.

Representative ketone solubilizing agents include but are not limitedto: 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone,cyclohexanone, cycloheptanone, 2-heptanone, 3-heptanone,5-methyl-2-hexanone, 2-octanone, 3-octanone, diisobutyl ketone,4-ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4-decanone,2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone.

Nitrile solubilizing agents of the present invention comprise nitrilesrepresented by the formula R¹CN, wherein R¹ is selected from aliphatic,alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms,and wherein said nitriles have a molecular weight of from about 90 toabout 200 atomic mass units. R¹ in said nitrile solubilizing agents ispreferably selected from aliphatic and alicyclic hydrocarbon radicalshaving 8 to 10 carbon atoms. The molecular weight of said nitrilesolubilizing agents is preferably from about 120 to about 140 atomicmass units. R¹ may optionally include substituted hydrocarbon radicals,that is, radicals containing non-hydrocarbon substituents selected fromhalogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R¹ mayoptionally include heteroatom-substituted hydrocarbon radicals, that is,radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-)or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.In general, no more than three non-hydrocarbon substituents andheteroatoms, and preferably no more than one, will be present for each10 carbon atoms in R¹, and the presence of any such non-hydrocarbonsubstituents and heteroatoms must be considered in applying theaforementioned molecular weight limitations. Representative R¹aliphatic, alicyclic and aryl hydrocarbon radicals in the generalformula R¹CN include pentyl, isopentyl, neopentyl, tert-pentyl,cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyland their configurational isomers, as well as phenyl, benzyl, cumenyl,mesityl, tolyl, xylyl and phenethyl. Representative nitrile solubilizingagents include but are not limited to: 1-cyanopentane,2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1-cyanoheptane,1-cyanooctane, 2-cyanooctane, 1-cyanononane, 1-cyanodecane,2-cyanodecane, 1-cyanoundecane and 1-cyanododecane.

Chlorocarbon solubilizing agents of the present invention comprisechlorocarbons represented by the formula RCl_(x), wherein; x is selectedfrom the integers 1 or 2; R is selected from aliphatic and alicyclichydrocarbon radicals having 1 to 12 carbon atoms; and wherein saidchlorocarbons have a molecular weight of from about 100 to about 200atomic mass units. The molecular weight of said chlorocarbonsolubilizing agents is preferably from about 120 to 150 atomic massunits. Representative R aliphatic and alicyclic hydrocarbon radicals inthe general formula RCl_(x) include methyl, ethyl, propyl, isopropyl,butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl,tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl and their configurational isomers.

Representative chlorocarbon solubilizing agents include but are notlimited to: 3-(chloromethyl)pentane, 3-chloro-3-methylpentane,1-chlorohexane, 1,6-dichlorohexane, 1-chloroheptane, 1-chlorooctane,1-chlorononane, 1-chlorodecane, and 1,1,1-trichlorodecane.

Ester solubilizing agents of the present invention comprise estersrepresented by the general formula R¹CO₂R², wherein R¹ and R² areindependently selected from linear and cyclic, saturated andunsaturated, alkyl and aryl radicals. Preferred esters consistessentially of the elements C, H and O, have a molecular weight of fromabout 80 to about 550 atomic mass units.

Representative esters include but are not limited to:(CH₃)₂CHCH₂OOC(CH₂)₂₋₄OCOCH₂CH(CH₃)₂ (diisobutyl dibasic ester), ethylhexanoate, ethyl heptanoate, n-butyl propionate, n-propyl propionate,ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester,dipropyl carbonate, “Exxate 700” (a commercial C₇ alkyl acetate),“Exxate 800” (a commercial C₈ alkyl acetate), dibutyl phthalate, andtert-butyl acetate.

Lactone solubilizing agents of the present invention comprise lactonesrepresented by structures [A], [B], and [C]:

These lactones contain the functional group —CO₂— in a ring of six (A),or preferably five atoms (B), wherein for structures [A] and [B], R₁through R₈ are independently selected from hydrogen or linear, branched,cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. EachR₁ though R₈ may be connected forming a ring with another R₁ through R₈.The lactone may have an exocyclic alkylidene group as in structure [C],wherein R₁ through R₆ are independently selected from hydrogen orlinear, branched, cyclic, bicyclic, saturated and unsaturatedhydrocarbyl radicals. Each R₁ though R₆ may be connected forming a ringwith another R₁ through R₆. The lactone solubilizing agents have amolecular weight range of from about 80 to about 300 atomic mass units,preferred from about 80 to about 200 atomic mass units.

Representative lactone solubilizing agents include but are not limitedto the compounds listed in Table 4.

TABLE 4 Molecular Molecular Additive Molecular Structure Formula Weight(amu) (E,Z)-3-ethylidene-5-methyl-dihydro-furan-2-one

C₇H₁₀O₂ 126 (E,Z)-3-propylidene-5-methyl-dihydro-furan-2-one

C₈H₁₂O₂ 140 (E,Z)-3-butylidene-5-methyl-dihydro-furan-2-one

C₉H₁₄O₂ 154 (E,Z)-3-pentylidene-5-methyl-dihydro-furan-2-one

C₁₀H₁₆O₂ 168 (E,Z)-3-Hexylidene-5-methyl-dihydro-furan-2-one

C₁₁H₁₈O₂ 182 (E,Z)-3-Heptylidene-5-methyl-dihydro-furan-2-one

C₁₂H₂₀O₂ 196 (E,Z)-3-octylidene-5-methyl-dihydro-furan-2-one

C₁₃H₂₂O₂ 210 (E,Z)-3-nonylidene-5-methyl-dihydro-furan-2-one

C₁₄H₂₄O₂ 224 (E,Z)-3-decylidene-5-methyl-dihydro-furan-2-one

C₁₅H₂₆O₂ 238(E,Z)-3-(3,5,5-trimethylhexylidene)-5-methyl-dihydrofuran-2-one

C₁₄H₂₄O₂ 224 (E,Z)-3-cyclohexylmethylidene-5-methyl-dihydrofuran-2-one

C₁₂H₁₈O₂ 194 gamma-octalactone

C₁₈H₁₄O₂ 142 gamma-nonalactone

C₉H₁₆O₂ 156 gamma-decalactone

C₁₀H₁₈O₂ 170 gamma-undecalactone

C₁₁H₂₀O₂ 184 gamma-dodecalactone

C₁₂H₂₂O₂ 198 3-hexyldihydro-furan-2-one

C₁₀H₁₈O₂ 170 3-heptyldihydro-furan-2-one

C₁₁H₂₀O₂ 184 cis-3-ethyl-5-methyl-dihydro-furan-2-one

C₇H₁₂O₂ 128 cis-(3-propyl-5-methyl)-dihydro-furan-2-one

C₈H₁₄O₂ 142 cis-(3-butyl-5-methyl)-dihydro-furan-2-one

C₉H₁₆O₂ 156 cis-(3-pentyl-5-methyl)-dihydro-furan-2-one

C₁₀H₁₈O₂ 170 cis-3-hexyl-5-methyl-dihydro-furan-2-one

C₁₁H₂₀O₂ 184 cis-3-heptyl-5-methyl-dihydro-furan-2-one

C₁₂H₂₂O₂ 198 cis-3-octyl-5-methyl-dihydro-furan-2-one

C₁₃H₂₄O₂ 212 cis-3-(3,5,5,-trimethylhexyl)-5-methyl-dihydro-furan-2-one

C₁₄H₂₆O₂ 226 cis-3-cyclohexylmethyl-5-methyl-dihydro-furan-2-one

C₁₂H₂₀O₂ 196 5-methyl-5-hexyl-dihydro-furan-2-one

C₁₁H₂₀O₂ 184 5-methyl-5-octyl-dihydro-furan-2-one

C₁₃H₂₄O₂ 212 Hexahydro-isobenzofuran-1-one

C₈H₁₂O₂ 140 delta-decalactone

C₁₀H₁₈O₂ 170 delta-undecalactone

C₁₁H₂₀O₂ 184 delta-dodecalactone

C₁₂H₂₂O₂ 198 mixture of 4-hexyl-dihydrofuran-2-oneand3-hexyl-dihydro-furan-2-one

C₁₀H₁₈O₂ 170

Lactone solubilizing agents generally have a kinematic viscosity of lessthan about 7 centistokes at 40° C. For instance, gamma-undecalactone haskinematic viscosity of 5.4 centistokes andcis-(3-hexyl-5-methyl)dihydrofuran-2-one has viscosity of 4.5centistokes both at 40° C. Lactone solubilizing agents may be availablecommercially or prepared by methods as described in U.S. patentapplication Ser. No. 10/910,495 (inventors being P. J. Fagan and C. J.Brandenburg), filed Aug. 3, 2004, incorporated herein by reference.

Aryl ether solubilizing agents of the present invention further comprisearyl ethers represented by the formula R¹OR², wherein: R¹ is selectedfrom aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R² isselected from aliphatic hydrocarbon radicals having from 1 to 4 carbonatoms; and wherein said aryl ethers have a molecular weight of fromabout 100 to about 150 atomic mass units. Representative R¹ arylradicals in the general formula R¹OR² include phenyl, biphenyl, cumenyl,mesityl, tolyl, xylyl, naphthyl and pyridyl. Representative R² aliphatichydrocarbon radicals in the general formula R¹OR² include methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.Representative aromatic ether solubilizing agents include but are notlimited to: methyl phenyl ether (anisole), 1,3-dimethyoxybenzene, ethylphenyl ether and butyl phenyl ether.

Fluoroether solubilizing agents of the present invention comprise thoserepresented by the general formula R¹OCF₂CF₂H, wherein R¹ is selectedfrom aliphatic and alicyclic hydrocarbon radicals having from about 5 toabout 15 carbon atoms, preferably primary, linear, saturated, alkylradicals. Representative fluoroether solubilizing agents include but arenot limited to: C₈H₁₇OCF₂CF₂H and C₆H₁₃OCF₂CF₂H. It should be noted thatif the refrigerant is a fluoroether, then the solubilizing agent may notbe the same fluoroether.

Fluoroether solubilizing agents may further comprise ethers derived fromfluoro-olefins and polyols. The fluoro-olefins may be of the typeCF₂═CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine,fluorine, CF₃ or OR_(f), wherein R_(f) is CF₃, C₂F₅, or C₃F₇.Representative fluoro-olefins are tetrafluoroethylene,chlorotrifluoroethylene, hexafluoropropylene, and perfluoromethylvinylether. The polyols may be of the typeHOCH₂CRR′(CH₂)z(CHOH)_(x)CH₂(CH₂OH)_(y), wherein R and R′ are hydrogenor CH₃ or C₂H₅ and wherein x is an integer from 0-4, y is an integerfrom 0-3 and z is either zero or 1. Representative polyols aretrimethylol propane, pentaerythritol, butane diol, and ethylene glycol.

1,1,1-Trifluoroalkane solubilizing agents of the present inventioncomprise 1,1,1-trifluoroalkanes represented by the general formulaCF₃R¹, wherein R¹ is selected from aliphatic and alicyclic hydrocarbonradicals having from about 5 to about 15 carbon atoms, preferablyprimary, linear, saturated, alkyl radicals. Representative1,1,1-trifluoroalkane solubilizing agents include but are not limitedto: 1,1,1-trifluorohexane and 1,1,1-trifluorododecane.

Solubilizing agents of the present invention may be present as a singlecompound, or may be present as a mixture of more than one solubilizingagent. Mixtures of solubilizing agents may contain two solubilizingagents from the same class of compounds, say two lactones, or twosolubilizing agents from two different classes, such as a lactone and apolyoxyalkylene glycol ether.

In the present compositions comprising refrigerant and UV fluorescentdye, or comprising heat transfer fluid and UV fluorescent dye, fromabout 0.001 weight percent to about 1.0 weight percent of thecomposition is UV dye, preferably from about 0.005 weight percent toabout 0.5 weight percent, and most preferably from 0.01 weight percentto about 0.25 weight percent.

Solubility of these UV fluorescent dyes in refrigerant and heat transfercompositions may be poor. Therefore, methods for introducing these dyesinto the refrigeration or air conditioning apparatus have been awkward,costly and time consuming. U.S. Pat. No. RE 36,951 describes a method,which utilizes a dye powder, solid pellet or slurry of dye that may beinserted into a component of the refrigeration or air conditioningapparatus. As refrigerant and lubricant are circulated through theapparatus, the dye is dissolved or dispersed and carried throughout theapparatus. Numerous other methods for introducing dye into arefrigeration or air conditioning apparatus are described in theliterature.

Ideally, the UV fluorescent dye could be dissolved in the refrigerantitself thereby not requiring any specialized method for introduction tothe refrigeration or air conditioning apparatus. The present inventionrelates to compositions including UV fluorescent dye, which may beintroduced into the system in the refrigerant. The inventivecompositions will allow the storage and transport of dye-containingrefrigerant and heat transfer fluid even at low temperatures whilemaintaining the dye in solution.

In the present compositions comprising refrigerant, UV fluorescent dyeand solubilizing agent, or comprising heat transfer fluid and UVfluorescent dye and solubilizing agent, from about 1 to about 50 weightpercent, preferably from about 2 to about 25 weight percent, and mostpreferably from about 5 to about 15 weight percent of the combinedcomposition is solubilizing agent in the refrigerant or heat transferfluid. In the compositions of the present invention the UV fluorescentdye is present in a concentration from about 0.001 weight percent toabout 1.0 weight percent in the refrigerant or heat transfer fluid,preferably from 0.005 weight percent to about 0.5 weight percent, andmost preferably from 0.01 weight percent to about 0.25 weight percent.

Optionally, commonly used refrigeration or air-conditioning systemadditives may be added, as desired, to compositions of the presentinvention in order to enhance performance and system stability. Theseadditives are known in the field of refrigeration and air-conditioning,and include, but are not limited to, anti wear agents, extreme pressurelubricants, corrosion and oxidation inhibitors, metal surfacedeactivators, free radical scavengers, and foam control agents. Ingeneral, these additives are present in the inventive compositions insmall amounts relative to the overall composition. Typicallyconcentrations of from less than about 0.1 weight percent to as much asabout 3 weight percent of each additive are used. These additives areselected on the basis of the individual system requirements. Theseadditives include members of the triaryl phosphate family of EP (extremepressure) lubricity additives, such as butylated triphenyl phosphates(BTPP), or other alkylated triaryl phosphate esters, e.g. Syn-0-Ad 8478from Akzo Chemicals, tricresyl phosphates and related compounds.Additionally, the metal dialkyl dithiophosphates (e.g. zinc dialkyldithiophosphate (or ZDDP), Lubrizol 1375 and other members of thisfamily of chemicals may be used in compositions of the presentinvention. Other antiwear additives include natural product oils andasymmetrical polyhydroxyl lubrication additives, such as Synergol TMS(International Lubricants). Similarly, stabilizers such as antioxidants, free radical scavengers, and water scavengers may be employed.Compounds in this category can include, but are not limited to,butylated hydroxy toluene (BHT) and epoxides.

Solubilizing agents such as ketones may have an objectionable odor,which can be masked by addition of an odor masking agent or fragrance.Typical examples of odor masking agents or fragrances may includeEvergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or OrangePeel all commercially available, as well as d-limonene and pinene. Suchodor masking agents may be used at concentrations of from about 0.001%to as much as about 15% by weight based on the combined weight of odormasking agent and solubilizing agent.

The present invention further relates to a method of using therefrigerant or heat transfer fluid compositions further comprisingultraviolet fluorescent dye, and optionally, solubilizing agent, inrefrigeration or air-conditioning apparatus. The method comprisesintroducing the refrigerant or heat transfer fluid composition into therefrigeration or air-conditioning apparatus. This may be done bydissolving the UV fluorescent dye in the refrigerant or heat transferfluid composition in the presence of a solubilizing agent andintroducing the combination into the apparatus. Alternatively, this maybe done by combining solubilizing agent and UV fluorescent dye andintroducing said combination into refrigeration or air conditioningapparatus containing refrigerant and/or heat transfer fluid. Theresulting composition may be used in the refrigeration or airconditioning apparatus.

The present invention further relates to a method of using therefrigerant or heat transfer fluid compositions comprising ultravioletfluorescent dye to detect leaks. The presence of the dye in thecompositions allows for detection of leaking refrigerant in therefrigeration or air conditioning apparatus. Leak detection helps toaddress, resolve or prevent inefficient operation of the apparatus orsystem or equipment failure. Leak detection also helps one containchemicals used in the operation of the apparatus.

The method comprises providing the composition comprising refrigerant,ultra-violet fluorescent dye or comprising heat transfer fluid and UVfluorescent dye, as described herein, and optionally, a solubilizingagent as described herein, to refrigeration and air-conditioningapparatus and employing a suitable means for detecting the UVfluorescent dye-containing refrigerant. Suitable means for detecting thedye include, but are not limited to, ultra-violet lamps, often referredto as a “black light” or “blue light”. Such ultra-violet lamps arecommercially available from numerous sources specifically designed forthis purpose. Once the ultra-violet fluorescent dye containingcomposition has been introduced to the refrigeration or air conditioningapparatus and has been allowed to circulate throughout the system, aleak can be found by shining said ultra-violet lamp on the apparatus andobserving the fluorescence of the dye in the vicinity of any leak point.

The present invention further relates to a method of using thecompositions of the present invention for producing refrigeration orheat, wherein the method comprises producing refrigeration byevaporating said composition in the vicinity of a body to be cooled andthereafter condensing said composition; or producing heat by condensingsaid composition in the vicinity of the body to be heated and thereafterevaporating said composition.

Mechanical refrigeration is primarily an application of thermodynamicswherein a cooling medium, such as a refrigerant, goes through a cycle sothat it can be recovered for reuse. Commonly used cycles includevapor-compression, absorption, steam-jet or steam-ejector, and air.

Vapor-compression refrigeration systems include an evaporator, acompressor, a condenser, and an expansion device. A vapor-compressioncycle re-uses refrigerant in multiple steps producing a cooling effectin one step and a heating effect in a different step. The cycle can bedescribed simply as follows. Liquid refrigerant enters an evaporatorthrough an expansion device, and the liquid refrigerant boils in theevaporator at a low temperature to form a gas and produce cooling. Thelow-pressure gas enters a compressor where the gas is compressed toraise its pressure and temperature. The higher-pressure (compressed)gaseous refrigerant then enters the condenser in which the refrigerantcondenses and discharges its heat to the environment. The refrigerantreturns to the expansion device through which the liquid expands fromthe higher-pressure level in the condenser to the low-pressure level inthe evaporator, thus repeating the cycle.

There are various types of compressors that may be used in refrigerationapplications. Compressors can be generally classified as reciprocating,rotary, jet, centrifugal, scroll, screw or axial-flow, depending on themechanical means to compress the fluid, or as positive-displacement(e.g., reciprocating, scroll or screw) or dynamic (e.g., centrifugal orjet), depending on how the mechanical elements act on the fluid to becompressed.

Either positive displacement or dynamic compressors may be used in thepresent inventive process. A centrifugal type compressor is thepreferred equipment for the present refrigerant compositions.

A centrifugal compressor uses rotating elements to accelerate therefrigerant radially, and typically includes an impeller and diffuserhoused in a casing. Centrifugal compressors usually take fluid in at animpeller eye, or central inlet of a circulating impeller, and accelerateit radially outward. Some static pressure rise occurs in the impeller,but most of the pressure rise occurs in the diffuser section of thecasing, where velocity is converted to static pressure. Eachimpeller-diffuser set is a stage of the compressor. Centrifugalcompressors are built with from 1 to 12 or more stages, depending on thefinal pressure desired and the volume of refrigerant to be handled.

The pressure ratio, or compression ratio, of a compressor is the ratioof absolute discharge pressure to the absolute inlet pressure. Pressuredelivered by a centrifugal compressor is practically constant over arelatively wide range of capacities.

Positive displacement compressors draw vapor into a chamber, and thechamber decreases in volume to compress the vapor. After beingcompressed, the vapor is forced from the chamber by further decreasingthe volume of the chamber to zero or nearly zero. A positivedisplacement compressor can build up a pressure, which is limited onlyby the volumetric efficiency and the strength of the parts to withstandthe pressure.

Unlike a positive displacement compressor, a centrifugal compressordepends entirely on the centrifugal force of the high-speed impeller tocompress the vapor passing through the impeller. There is no positivedisplacement, but rather what is called dynamic-compression.

The pressure a centrifugal compressor can develop depends on the tipspeed of the impeller. Tip speed is the speed of the impeller measuredat its tip and is related to the diameter of the impeller and itsrevolutions per minute. The capacity of the centrifugal compressor isdetermined by the size of the passages through the impeller. This makesthe size of the compressor more dependent on the pressure required thanthe capacity.

Because of its high-speed operation, a centrifugal compressor isfundamentally a high volume, low-pressure machine. A centrifugalcompressor works best with a low-pressure refrigerant, such astrichlorofluoromethane (CFC-11) or 1,2,2-trichlorotrifluoroethane(CFC-113).

Large centrifugal compressors typically operate at 3000 to 7000revolutions per minute (rpm). Small turbine centrifugal compressors aredesigned for high speeds, from about 40,000 to about 70,000 (rpm), andhave small impeller sizes, typically less than 0.15 meters.

A multi-stage impeller may be used in a centrifugal compressor toimprove compressor efficiency thus requiring less power in use. For atwo-stage system, in operation, the discharge of the first stageimpeller goes to the suction intake of a second impeller. Both impellersmay operate by use of a single shaft (or axle). Each stage can build upa compression ratio of about 4 to 1; that is, the absolute dischargepressure can be four times the absolute suction pressure. An example ofa two-stage centrifugal compressor system, in this case for automotiveapplications, is described in U.S. Pat. No. 5,065,990, incorporatedherein by reference.

The compositions of the present invention suitable for use in arefrigeration or air conditioning systems employing a centrifugalcompressor comprise at least one of:

-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-(difluoromethoxy)-1,1,2-trifluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-(difluoromethoxy)-1,2,2-trifluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2-fluoromethoxy-1,1,1,2-tetrafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-methoxy-1,1,2,2-tetrafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2-methoxy-1,1,1,2-tetrafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-difluoromethoxy-2,2-difluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2-methoxy-1,1,2-trifluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1-difluoro-2-methoxyethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,2,2-tetrafluoro-3-(trifluoromethoxy)propane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-(2,2-difluoroethoxy)-1,1,2,2,2-pentafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,3,3,3-hexafluoro-2-(trifluoromethoxy)propane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,2-trifluoro-1-methoxy-2-(trifluoromethoxy)ethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,2,3,3-hexafluoro-3-methoxypropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,3,3,3-hexafluoro-2-methoxypropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,2,2,3,3-hexafluoro-3-methoxypropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-(1,1,-difluoroethoxy)-1,1,2,2-tetrafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    3-(difluoromethoxy)-1,1,2,2-tetrafluoropropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,2,2-pentafluoro-3-methoxypropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2-(difluoromethoxy)-1,1,1-trifluoropropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2-ethoxy-1,1,1,2-tetrafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1-trifluoro-2-ethoxyethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1-trifluoro-3-methoxypropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1-trifluoro-2-methoxypropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-ethoxy-1,2,2-trifluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,2,3,3-hexafluoro-3-(pentafluoroethoxy)propane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2-ethoxy-1,1,1,2,3,3,3-heptafluoropropane:-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    3-ethoxy-1,1,1,2,2,3,3-heptafluoropropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-(1,1,2,2-tetrafluoroethoxy)propane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2,3-difluoro-4-(trifluoromethyl)oxetane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    C₄F₉OCH₃;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    C₄F₉OC₂H₅;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,2,2,3,3-heptafluoro-3-methoxypropane; or-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-ethoxy-1,1,2,2-tetrafluoroethane.

These above-listed compositions are also suitable for use in amulti-stage centrifugal compressor, preferably a two-stage centrifugalcompressor apparatus.

The compositions of the present invention may be used in stationaryair-conditioning, heat pumps or mobile air-conditioning andrefrigeration systems. Stationary air conditioning and heat pumpapplications include window, ductless, ducted, packaged terminal,chillers and commercial, including packaged rooftop. Refrigerationapplications include domestic or home refrigerators and freezers, icemachines, self-contained coolers and freezers, walk-in coolers andfreezers and transport refrigeration systems.

The compositions of the present invention may additionally be used inair-conditioning, heating and refrigeration systems that employ fin andtube heat exchangers, microchannel heat exchangers and vertical orhorizontal single pass tube or plate type heat exchangers.

Conventional microchannel heat exchangers may not be ideal for the lowpressure refrigerant compositions of the present invention. The lowoperating pressure and density result in high flow velocities and highfrictional losses in all components. In these cases, the evaporatordesign may be modified. Rather than several microchannel slabs connectedin series (with respect to the refrigerant path) a single slab/singlepass heat exchanger arrangement may be used. Therefore, a preferred heatexchanger for the low pressure refrigerants of the present invention isa single slab/single pass heat exchanger.

In addition to two-stage or other multi-stage centrifugal compressorapparatus, the following compositions of the present invention aresuitable for use in refrigeration or air conditioning apparatusemploying a single slab/single pass heat exchanger:

-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-(difluoromethoxy)-1,1,2-trifluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-(difluoromethoxy)-1,2,2-trifluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2-fluoromethoxy-1,1,1,2-tetrafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-methoxy-1,1,2,2-tetrafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2-methoxy-1,1,1,2-tetrafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-difluoromethoxy-2,2-difluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2-methoxy-1,1,2-trifluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1-difluoro-2-methoxyethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,2,2-tetrafluoro-3-(trifluoromethoxy)propane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-(2,2-difluoroethoxy)-1,1,2,2,2-pentafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    3-(difluoromethoxy)-1,1,1,2,2-pentafluoropropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,3,3,3-hexafluoro-2-(trifluoromethoxy)propane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,2-trifluoro-1-methoxy-2-(trifluoromethoxy)ethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,2,3,3-hexafluoro-3-methoxypropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,3,3,3-hexafluoro-2-methoxypropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,2,2,3,3-hexafluoro-3-methoxypropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-(1,1,-difluoroethoxy)-1,1,2,2-tetrafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    3-(difluoromethoxy)-1,1,2,2-tetrafluoropropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,2,2-pentafluoro-3-methoxypropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2-(difluoromethoxy)-1,1,1-trifluoropropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2-ethoxy-1,1,1,2-tetrafluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1-trifluoro-2-ethoxyethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1-trifluoro-3-methoxypropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1-trifluoro-2-methoxypropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-ethoxy-1,2,2-trifluoroethane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,2,3,3-hexafluoro-3-(pentafluoroethoxy)propane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2-ethoxy-1,1,1,2,3,3,3-heptafluoropropane:-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    3-ethoxy-1,1,1,2,2,3,3-heptafluoropropane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-(1,1,2,2-tetrafluoroethoxy)propane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    2,3-difluoro-4-(trifluoromethyl)oxetane;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    C₄F₉OCH₃;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    C₄F₉OC₂H₅;-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1,1,1,2,2,3,3-heptafluoro-3-methoxypropane; or-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and    1-ethoxy-1,1,2,2-tetrafluoroethane.

The compositions of the present invention are particularly useful insmall turbine centrifugal compressors, which can be used in auto andwindow air-conditioning or heat pumps as well as other applications.These high efficiency miniature centrifugal compressors may be driven byan electric motor and can therefore be operated independently of theengine speed. A constant compressor speed allows the system to provide arelatively constant cooling capacity at all engine speeds. This providesan opportunity for efficiency improvements especially at higher enginespeeds as compared to a conventional R-134a automobile air-conditioningsystem. When the cycling operation of conventional systems at highdriving speeds is taken into account, the advantage of these lowpressure systems becomes even greater.

Some of the low pressure refrigerant fluids of the present invention maybe suitable as drop-in replacements for CFC-113 in existing centrifugalequipment.

The present invention further relates to a process for producingrefrigeration comprising evaporating the compositions of the presentinvention in the vicinity of a body to be cooled, and thereaftercondensing said compositions.

The present invention further relates to a process for producing heatcomprising condensing the compositions of the present invention in thevicinity of a body to be heated, and thereafter evaporating saidcompositions.

The present invention further relates to a process for transfer of heatfrom a heat source to a heat sink wherein the compositions of thepresent invention serve as heat transfer fluids. Said process for heattransfer comprises transferring the compositions of the presentinvention from a heat source to a heat sink.

Heat transfer fluids are utilized to transfer, move or remove heat fromone space, location, object or body to a different space, location,object or body by radiation, conduction, or convection. A heat transferfluid may function as a secondary coolant by providing means of transferfor cooling (or heating) from a remote refrigeration (or heating)system. In some systems, the heat transfer fluid may remain in aconstant state throughout the transfer process (i.e., not evaporate orcondense). Alternatively, evaporative cooling processes may utilize heattransfer fluids as well.

A heat source may be defined as any space, location, object or body fromwhich it is desirable to transfer, move or remove heat. Examples of heatsources may be spaces (open or enclosed) requiring refrigeration orcooling, such as refrigerator or freezer cases in a supermarket,building spaces requiring air-conditioning, or the passenger compartmentof an automobile requiring air-conditioning. A heat sink may be definedas any space, location, object or body capable of absorbing heat. Avapor compression refrigeration system is one example of such a heatsink.

EXAMPLES Example 1 Impact of Vapor Leakage

A vessel is charged with an initial composition at a specifiedtemperature, and the initial vapor pressure of the composition ismeasured. The composition is allowed to leak from the vessel, while thetemperature is held constant, until 50 weight percent of the initialcomposition is removed, at which time the vapor pressure of thecomposition remaining in the vessel is measured. Mathematicallypredicted results are summarized in Table 5 below.

TABLE 5 Compounds After 50% After 50% wt % A/ Initial Initial Leak LeakDelta wt % B Psia kPa Psia kPa P % PEIK/HFOC-245caEαβ (34.7° C.)47.6/52.4 14.70 101.35 14.70 101.35 0.0% 60/40 14.60 100.66 14.45 99.631.0% 79/21 13.70 94.46 12.39 85.43 9.6% 80/20 13.60 93.77 12.21 84.1910.2% 100/0  8.72 60.12 8.72 60.12 0.0% 20/80 14.22 98.04 13.38 92.255.9% 10/90 13.58 93.63 12.54 86.46 7.7%  1/99 12.39 85.43 12.21 84.191.5%  0/100 12.19 84.05 12.19 84.05 0.0% PEIK/HFOC-245eaE (40.5° C.)66.2/33.8 14.71 101.42 14.71 101.42 0.0% 80/20 14.67 101.15 14.12 97.353.7% 90/10 13.60 93.77 12.57 86.67 7.6% 99/1  11.29 77.84 10.97 75.642.8% 100/0  10.85 74.81 10.85 74.81 0.0% 40/60 14.36 99.01 13.37 92.186.9% 38/62 14.31 98.66 13.02 89.77 9.0% 37/63 14.28 98.46 12.82 88.3910.2%  0/100 9.47 65.29 9.47 65.29 0.0% PEIK/HFOC-245ebEβγ (36.2° C.)52.4/47.6 14.70 101.35 14.70 101.35 0.0% 80/20 13.86 95.56 12.76 87.987.9% 82/18 13.67 94.25 12.39 85.43 9.4% 83/17 13.56 93.49 12.20 84.1210.0% 100/0  9.24 63.71 9.24 63.71 0.0% 20/80 14.05 96.87 12.65 87.2210.0%  0/100 11.57 79.77 11.57 79.77 0.0% PEIK/HFOC-254cbEβγ (27.4° C.)59.7/40.3 14.72 101.49 14.72 101.49 0.0% 80/20 14.60 100.66 13.84 95.425.2% 82/18 14.57 100.46 13.11 90.39 10.0% 100/0  6.53 45.02 6.53 45.020.0% 40/60 14.59 100.60 13.84 95.42 5.1% 36/64 14.52 100.11 13.16 90.749.4% 35/65 14.49 99.91 12.96 89.36 10.6%  0/100 10.38 71.57 10.38 71.570.0% PEIK/HFOC-254ebEβγ (29.9° C.) 63.6/36.4 14.70 101.35 14.70 101.350.0% 80/20 14.55 100.32 14.25 98.25 2.1% 85/15 14.44 99.56 13.20 91.018.6% 86/14 14.41 99.35 12.37 85.29 14.2% 100/0  7.22 49.78 7.22 49.780.0% 40/60 14.32 98.73 13.55 93.42 5.4% 29/71 13.82 95.29 12.48 86.059.7% 28/72 13.77 94.94 12.39 85.43 10.0%  0/100 11.05 76.19 11.05 76.190.0% PEIK/HFOC-254faE (35.9° C.) 73.3/26.7 14.68 101.22 14.68 101.220.0% 80/20 14.66 101.08 14.59 100.60 0.5% 87/13 14.54 100.25 13.45 92.747.5% 88/19 14.50 99.97 12.97 89.43 10.6% 100/0  9.13 62.95 9.13 62.950.0% 49/51 14.61 100.73 13.43 92.60 8.1% 48/52 14.60 100.66 12.96 89.3611.2%  0/100 7.38 50.88 7.38 50.88 0.0% PEIK/HFOC-263ebEβγ (34.4° C.)79.4/20.6 14.72 101.49 14.72 101.49 0.0% 90/10 14.71 101.42 14.68 101.220.2% 91/9  14.71 101.42 14.56 100.39 1.0% 100/0  8.62 59.43 8.62 59.430.0% 60/40 14.66 101.08 13.88 95.70 5.3% 58/42 14.64 100.94 13.41 92.468.4% 54/43 14.63 100.87 13.08 90.18 10.6%  0/100 6.89 47.51 6.89 47.510.0% PEIK/HFOC-272fbEβγ (31.5° C.) 75.3/24.7 14.72 101.49 14.72 101.490.0% 89/11 14.66 101.08 13.50 93.08 7.9% 90/10 14.64 100.94 12.30 84.8116.0% 100/0  7.70 53.09 7.70 53.09 0.0% 60/40 14.70 101.35 14.56 100.391.0% 53/47 14.68 101.22 13.34 91.98 9.1% 52/48 14.68 101.22 12.72 87.7013.4%  0/100 8.07 55.64 8.07 55.64 0.0% PEIK/HFOC-347mfcEαβ (38.6° C.)58.8/41.2 14.72 101.49 14.72 101.49 0.0% 80/20 14.27 98.39 13.53 93.295.2% 85/15 13.92 95.98 12.59 86.81 9.6% 86/14 13.82 95.29 12.36 85.2210.6% 100/0  10.11 69.71 10.11 69.71 0.0% 40/60 14.46 99.70 14.12 97.352.4% 20/80 13.46 92.80 12.48 86.05 7.3% 10/90 12.56 86.60 11.74 80.946.5%  1/99 11.42 78.74 11.31 77.98 1.0%  0/100 11.27 77.70 11.27 77.700.0% PEIK/HFOC-347mcfEβγ (38.2° C.) 57.8/42.2 14.70 101.35 14.70 101.350.0% 80/20 14.22 98.04 13.41 92.46 5.7% 84/16 13.94 96.11 12.65 87.229.3% 85/15 13.85 95.49 12.42 85.63 10.3% 100/0  9.96 68.67 9.96 68.670.0% 40/60 14.47 99.77 14.17 97.70 2.1% 20/80 13.51 93.15 12.59 86.816.8% 10/90 12.64 87.15 11.87 81.84 6.1%  1/99 11.53 79.50 11.43 78.810.9%  0/100 11.39 78.53 11.39 78.53 0.0% PEIK/HFOC-347mcfEγδ (38.4° C.)58.5/41.5 14.67 101.15 14.67 101.15 0.0% 80/20 14.21 97.98 13.45 92.745.3% 85/15 13.86 95.56 12.50 86.19 9.8% 86/14 13.76 94.87 12.27 84.6010.8% 100/0  10.04 69.22 10.04 69.22 0.0% 40/60 14.41 99.35 14.09 97.152.2% 20/80 13.43 92.60 12.47 85.98 7.1% 10/90 12.54 86.46 11.74 80.946.4%  1/99 11.42 78.74 11.31 77.98 1.0%  0/100 11.27 77.70 11.27 77.700.0% PEIK/HFOC-347mmzEβγ (44.8° C.) 78.0/22.0 14.70 101.35 14.70 101.350.0% 90/10 14.42 99.42 14.12 97.35 2.1% 99/1  13.04 89.91 12.80 88.251.8% 100/0  12.69 87.50 12.69 87.50 0.0% 60/40 14.37 99.08 13.98 96.392.7% 40/60 13.35 92.05 12.06 83.15 9.7% 39/61 13.28 91.56 11.96 82.469.9% 38/62 13.21 91.08 11.85 81.70 10.3%  0/100 9.30 64.12 9.30 64.120.0% PEIK/HFOC-356mecE2αβγδ (47.6° C.) 78.6/21.4 14.71 101.42 14.71101.42 0.0% 90/10 14.55 100.32 14.51 100.04 0.3% 99/1  14.09 97.15 14.0797.01 0.1% 100/0  14.01 96.60 14.01 96.60 0.0% 40/60 13.71 94.53 13.0389.84 5.0% 20/80 12.46 85.91 11.24 77.50 9.8% 10/90 11.50 79.29 10.5572.74 8.3%  1/99 10.30 71.02 10.17 70.12 1.3%  0/100 10.15 69.98 10.1569.98 0.0% PEIK/HFOC-356mecEγδ (38.8° C.) 73.7/26.3 14.68 101.22 14.68101.22 0.0% 88/12 14.49 99.91 13.50 93.08 6.8% 89/11 14.46 99.70 12.9689.36 10.4% 100/0  10.19 70.26 10.19 70.26 0.0% 47/53 14.10 97.22 12.7287.70 9.8% 46/54 14.05 96.87 12.57 86.67 10.5%  0/100 8.59 59.23 8.5959.23 0.0% PEIK/HFOC-356mmzEβγ (40.8° C.) 71.0/29.0 14.72 101.49 14.72101.49 0.0% 90/10 14.11 97.29 12.89 88.87 8.6% 91/9  14.01 96.60 12.5986.81 10.1% 100/0  10.97 75.64 10.97 75.64 0.0% 40/60 13.88 95.70 12.8788.74 7.3% 32/68 13.38 92.25 12.06 83.15 9.9% 31/69 13.31 91.77 11.9782.53 10.1%  0/100 10.10 69.64 10.10 69.64 0.0% PEIK/HFOC-356pccEγδ(42.9° C.) 80.6/19.4 14.69 101.28 14.69 101.28 0.0% 90/10 14.54 100.2514.04 96.80 3.4% 95/5  14.06 96.94 12.55 86.53 10.7% 94/6  14.21 97.9812.85 88.60 9.6% 60/40 14.43 99.49 13.55 93.42 6.1% 57/43 14.35 98.9413.07 90.12 8.9% 56/44 14.32 98.73 12.87 88.74 10.1% PEIK/HFOC-356pcfEβγ(45.8° C.) 86.5/13.5 14.68 101.22 14.68 101.22 0.0% 95/5  14.37 99.0813.98 96.39 2.7% 99/1  13.56 93.49 13.27 91.49 2.1% 70/30 14.46 99.7014.08 97.08 2.6% 60/40 14.24 98.18 12.87 88.74 9.6% 59/41 14.22 98.0412.65 87.22 11.0% PEIK/HFOC-356pcfEγδ (45.8° C.) 83.4/16.6 14.70 101.3514.70 101.35 0.0% 95/5  14.21 97.98 13.87 95.63 2.4% 99/1  13.46 92.8013.28 91.56 1.3% 60/40 14.27 98.39 13.46 92.80 5.7% 56/44 14.15 97.5612.88 88.81 9.0% 55/45 14.12 97.35 12.69 87.50 10.1% PEIK/HFOC-365mcEγδ(38.5° C.) 69.0/31.0 14.68 101.22 14.68 101.22 0.0% 88/12 14.20 97.9112.89 88.87 9.2% 89/11 14.12 97.35 12.52 86.32 11.3% 100/0  10.07 69.4310.07 69.43 0.0% 40/60 13.98 96.39 13.05 89.98 6.7% 29/71 13.32 91.8412.02 82.88 9.8% 28/72 13.25 91.36 11.93 82.25 10.0%  0/100 10.45 72.0510.45 72.05 0.0% PEIK/HFOC-365mpzEβγ (43.0° C.) 70.3/29.7 14.72 101.4914.72 101.49 0.0% 90/10 14.10 97.22 13.62 93.91 3.4% 99/1  12.35 85.1512.01 82.81 2.8% 100/0  11.89 81.98 11.89 81.98 0.0% 40/60 14.10 97.2213.86 95.56 1.7% 20/80 13.30 91.70 13.04 89.91 2.0% 10/90 12.85 88.6012.68 87.43 1.3%  1/99 12.42 85.63 12.40 85.50 0.2%  0/100 12.37 85.2912.37 85.29 0.0% PEIK/HFOC-374mefEβγ (41.0° C.) 79.6/20.4 14.70 101.3514.70 101.35 0.0% 90/10 14.51 100.04 13.89 95.77 4.3% 92/8  14.37 99.0813.17 90.80 8.4% 93/7  14.28 98.46 12.70 87.56 11.1% 100/0  11.05 76.1911.05 76.19 0.0% 60/40 14.34 98.87 13.48 92.94 6.0% 55/45 14.14 97.4912.77 88.05 9.7% 54/46 14.10 97.22 12.61 86.94 10.6%  0/100 8.18 56.408.18 56.40 0.0% PEIK/HFOC-383mEβγ (39.2° C.) 73.4/26.6 14.70 101.3514.70 101.35 0.0% 90/10 14.16 97.63 12.98 89.49 8.3% 91/9  14.04 96.8012.64 87.15 10.0% 100/0  10.34 71.29 10.34 71.29 0.0% 41/59 13.83 95.3612.49 86.12 9.7% 40/60 13.78 95.01 12.38 85.36 10.2%  0/100 10.16 70.0510.16 70.05 0.0% PEIK/HFOC-383mEγδ (39.0° C.) 78.3/21.7 14.67 101.1514.67 101.15 0.0% 90/10 14.45 99.63 13.56 93.49 6.2% 91/9  14.39 99.2213.11 90.39 8.9% 92/8  14.31 98.66 12.55 86.53 12.3% 100/0  10.26 70.7410.26 70.74 0.0% 60/40 14.40 99.29 13.62 93.91 5.4% 55/45 14.23 98.1112.91 89.01 9.3% 54/46 14.19 97.84 12.74 87.84 10.2%  0/100 8.49 58.548.49 58.54 0.0% PEIK/HFOC-383mzEβγ (36.0° C.) 72.4/27.6 14.71 101.4214.71 101.42 0.0% 88/12 14.43 99.49 13.21 91.08 8.5% 89/11 14.38 99.1512.69 87.50 11.8% 100/0  9.16 63.16 9.16 63.16 0.0% 45/55 14.14 97.4912.77 88.05 9.7% 44/56 14.09 97.15 12.63 87.08 10.4%  0/100 9.80 67.579.80 67.57 0.0% PEIK/HFOC-383peEβγ (34.5° C.) 76.0/24.0 14.71 101.4214.71 101.42 0.0% 89/11 14.66 101.08 13.97 96.32 4.7% 90/10 14.65 101.0112.13 83.63 17.2% 100/0  8.65 59.64 8.65 59.64 0.0% 54/46 14.52 100.1113.14 90.60 9.5% 53/47 14.49 99.91 12.92 89.08 10.8%  0/100 7.90 54.477.90 54.47 0.0% PEIK/HFOC-42-11meEβγ (50.0° C.)  0/100 20.83 143.6220.83 143.62 0.0%  1/99 20.78 143.27 20.77 143.20 0.0% 20/80 19.90137.21 19.75 136.17 0.8% 40/60 18.89 130.24 18.62 128.38 1.4% 60/4017.78 122.59 17.46 120.38 1.8% 80/20 16.56 114.18 16.32 112.52 1.4%99/1  15.30 105.49 15.28 105.35 0.1% 100/0  15.23 105.01 15.23 105.010.0% PEIK/HFOC-467mmyEβγ (40.7° C.) 58.0/42.0 14.68 101.22 14.68 101.220.0% 80/20 14.22 98.04 13.78 95.01 3.1% 90/10 13.42 92.53 12.28 84.678.5% 99/1  11.36 78.32 11.00 75.84 3.2% 100/0  10.93 75.36 10.93 75.360.0% 40/60 14.46 99.70 14.31 98.66 1.0% 20/80 13.70 94.46 13.38 92.252.3% 10/90 13.13 90.53 12.88 88.81 1.9%  1/99 12.51 86.25 12.48 86.050.2%  0/100 12.43 85.70 12.43 85.70 0.0% PEIK/HFOC-467mccEγδ (43.4° C.)68.9/31.1 14.70 101.35 14.70 101.35 0.0% 90/10 14.01 96.60 13.43 92.604.1% 99/1  12.41 85.56 12.16 83.84 2.0% 100/0  12.07 83.22 12.07 83.220.0% 40/60 14.03 96.73 13.55 93.42 3.4% 20/80 12.85 88.60 12.17 83.915.3% 10/90 12.05 83.08 11.57 79.77 4.0%  1/99 11.21 77.29 11.15 76.880.5%  0/100 11.11 76.60 11.11 76.60 0.0% PEIK/HFOC-494pcEβγ (44.8° C.)85.3/14.7 14.69 101.28 14.69 101.28 0.0% 95/5  14.29 98.53 13.68 94.324.3% 99/1  13.24 91.29 12.81 88.32 3.2% 100/0  12.69 87.50 12.69 87.500.0% 62/38 14.26 98.32 12.94 89.22 9.3% 61/39 14.23 98.11 12.74 87.8410.5%  0/100 5.74 39.58 5.74 39.58 0.0% PEIK/HFOC-c345mzeEαβ (41.3° C.)78.8/21.2 14.70 101.35 14.70 101.35 0.0% 90/10 14.49 99.91 13.77 94.945.0% 92/8  14.35 98.94 13.03 89.84 9.2% 93/7  14.25 98.25 12.58 86.7411.7% 100/0  11.18 77.08 11.18 77.08 0.0% 60/40 14.39 99.22 13.64 94.055.2% 54/46 14.15 97.56 12.81 88.32 9.5% 53/47 14.11 97.29 12.66 87.2910.3%  0/100 8.02 55.30 8.02 55.30 0.0% PEIK/C₄F₉OCH₃ (45.2° C.)77.0/23.0 14.70 101.35 14.70 101.35 0.0% 90/10 14.41 99.35 14.09 97.152.2% 99/1  13.18 90.87 12.96 89.36 1.7% 100/0  12.87 88.74 12.87 88.740.0% 60/40 14.43 99.49 14.10 97.22 2.3% 40/60 13.44 92.67 12.14 83.709.7% 39/61 13.37 92.18 12.02 82.88 10.1%  0/100 8.83 60.88 8.83 60.880.0% PEIK/C₄F₉OC₂H₅ (48.9° C.) 96.6/3.4 14.71 101.42 14.71 101.42 0.0%99/1  14.69 101.28 14.68 101.22 0.1% 100/0  14.66 101.08 14.66 101.080.0% 80/20 14.24 98.18 13.91 95.91 2.3% 63/37 13.29 91.63 12.02 82.889.6% 62/38 13.23 91.22 11.88 81.91 10.2%  0/100 5.74 39.58 5.74 39.580.0% PEIK/HFOC-347mccEγδ (32.1° C.) 39.5/60.5 14.71 101.42 14.71 101.420.0% 60/40 14.45 99.63 14.21 97.98 1.7% 76/24 13.82 95.29 12.58 86.749.0% 77/23 13.76 94.87 12.37 85.29 10.1% 100/0  7.88 54.33 7.88 54.330.0% 20/80 14.46 99.70 14.37 99.08 0.6% 10/90 14.13 97.42 14.02 96.670.8%  1/99 13.71 94.53 13.69 94.39 0.1%  0/100 13.65 94.11 13.65 94.110.0% PEIK/HFOC-374pcEβγ (39.9° C.) 74.8/25.2 14.69 101.28 14.69 101.280.0% 90/10 14.25 98.25 13.03 89.84 8.6% 91/9  14.15 97.56 12.67 87.3610.5% 60/40 14.54 100.25 14.17 97.70 2.5% 50/50 14.29 98.53 12.95 89.299.4% 49/51 14.26 98.32 12.77 88.05 10.4% 100/0  10.61 73.15 10.61 73.150.0%  0/100 8.42 58.05 8.42 58.05 0.0%

The results show the difference in vapor pressure between the originalcomposition and the composition remaining after 50 weight percent hasbeen removed is less then about 10 percent for compositions of thepresent invention. This indicates compositions of the present inventionare azeotropic or near-azeotropic. Where an azeotrope is present, thedata show compositions of the present invention have an initial vaporpressure higher than the vapor pressure of either pure component.

Example 2 Tip Speed to Develop Pressure

Tip speed can be estimated by making some fundamental relationships forrefrigeration equipment that use centrifugal compressors. The torque animpeller ideally imparts to a gas is defined asT=m*(v ₂ *r ₂ −v ₁ *r ₁)  Equation 1where

T=torque, N*m

m=mass rate of flow, kg/s

v₂=tangential velocity of refrigerant leaving impeller (tip speed), m/s

r₂=radius of exit impeller, m

v₁=tangential velocity of refrigerant entering impeller, m/s

r₁=radius of inlet of impeller, m

Assuming the refrigerant enters the impeller in an essentially radialdirection, the tangential component of the velocity v1=0, thereforeT=m*v ₂ *r ₂  Equation 2

The power required at the shaft is the product of the torque and therotative speedP=T*w  Equation 3where

P=power, W

w=rotative speed, rez/s therefore,P=T*w=m*v ₂ *r ₂ *w  Equation 4

At low refrigerant flow rates, the tip speed of the impeller and thetangential velocity of the refrigerant are nearly identical; thereforer ₂ *w=v ₂  Equation 5andP=m*v ₂ *v ₂  Equation 6

Another expression for ideal power is the product of the mass rate offlow and the isentropic work of compression,P=m*H _(i)*(1000J/kJ)  Equation 7where

H_(i)=Difference in enthalpy of the refrigerant from a saturated vaporat the evaporating conditions to saturated condensing conditions, kJ/kg.

Combining the two expressions Equation 6 and 7 produces,v ₂ *v ₂=1000*H _(i)  Equation 8

Although Equation 8 is based on some fundamental assumptions, itprovides a good estimate of the tip speed of the impeller and providesan important way to compare tip speeds of refrigerants.

The table below shows theoretical tip speeds that are calculated for1,2,2-trichlorotrifluoroethane (CFC-113) and compositions of the presentinvention. The conditions assumed for this comparison are:

Evaporator temperature 40.0° F. (4.4° C.) Condenser temperature 110.0°F. (43.3° C.) Liquid subcool temperature 10.0° F. (5.5° C.) Return gastemperature  75.0° F. (23.8° C.) Compressor efficiency is 70%

These are typical conditions under which small turbine centrifugalcompressors perform.

TABLE 6 Refrigerant Wt % Hi V2 V2 rel Composition PEIK Wt % B Btu/lbHi * 0.7 Btu/lb Hi * 0.7 KJ/Kg m/s to CFC-113 CFC-113 100 10.92 7.6 17.8133.3 na PEIK plus B: HFOC-245caEαβ 47.6 52.4 12.13 8.5 19.8 140.5 105%HFOC-245eaE 66.2 33.8 11.83 8.3 19.3 138.8 104% HFOC-245ebEβγ 52.4 47.612.03 8.4 19.6 140.0 105% HFOC-254cbEβγ 59.7 40.3 11.84 8.3 19.3 138.8104% HFOC-254ebEβγ 63.6 36.4 11.9 8.3 19.4 139.2 104% HFOC-254faE 73.326.7 11.76 8.2 19.1 138.4 104% HFOC-263ebEβγ 79.4 20.6 11.88 8.3 19.3139.1 104% HFOC-272fbEβγ 75.3 24.7 12.39 8.7 20.2 142.0 107%HFOC-347mccEγδ 39.5 60.5 12.04 8.4 19.6 140.0 105% HFOC-347mfcEαβ 58.841.2 11.84 8.3 19.3 138.8 104% HFOC-347mcfEβγ 57.8 42.2 11.84 8.3 19.3138.8 104% HFOC-347mcfEγδ 58.5 41.5 11.84 8.3 19.3 138.8 104%HFOC-347mmzEβγ 78.0 22.0 11.75 8.2 19.1 138.3 104% HFOC-356mecE2αβγδ78.6 21.4 11.95 8.4 19.5 139.5 105% HFOC-356mecEγδ 73.7 26.3 11.77 8.219.2 138.4 104% HFOC-356mmzEβγ 71 29.0 11.92 8.3 19.4 139.3 104%HFOC-365mcEγδ 69.0 31.0 12.23 8.6 19.9 141.1 106% HFOC-365mpzEβγ 70.329.7 12.18 8.5 19.8 140.8 106% HFOC-374mefEβγ 79.6 20.4 12.12 8.5 19.7140.5 105% HFOC-374pcEβγ 74.8 25.2 12.28 8.6 20.0 141.4 106%HFOC-383mEβγ 73.4 26.6 12.79 9.0 20.8 144.3 108% HFOC-383mEγδ 78.3 21.712.47 8.7 20.3 142.5 107% HFOC-383mzEβγ 72.4 27.6 12.6 8.8 20.5 143.2107% HFOC-383peEβγ 76 24 12.35 8.6 20.1 141.8 106% HFOC-467mmyEβγ 58 4212.37 8.7 20.1 141.9 106% HFOC-467mccEγδ 68.9 31.1 12.19 8.5 19.8 140.9106% HFOC-494pcEβγ 85.3 14.7 12.19 8.5 19.8 140.9 106% HFOC-C345mzeEαβ78.8 21.2 11.72 8.2 19.1 138.1 104% C₄F₉OCH₃ 77 23 11.76 8.2 19.1 138.4104% C₄F₉OC₂H₅ 96.6 3.4 11.68 8.2 19.0 137.9 103% HFOC-356pccEγδ 80.619.4 11.76 8.2 19.1 138.4 104% HFOC-356pcfEβγ 86.5 13.5 11.72 8.2 19.1138.1 104% HFOC-356pcfEγδ 83.4 16.6 11.8 8.3 19.2 138.6 104%

The Example shows that compounds of the present invention have tipspeeds within about +/−10 percent of CFC-113 and would be effectivereplacements for CFC-113 with minimal compressor design changes.

Example 3 Performance Data

The following table shows the performance of various refrigerantscompared to CFC-113. The data are based on the following conditions.

Evaporator temperature 40.0° F. (4.4° C.) Condenser temperature 110.0°F. (43.3° C.) Subcool temperature 10.0° F. (5.5° C.) Return gastemperature  75.0° F. (23.8° C.) Compressor efficiency is 70%

TABLE 7 Compr Compr Evap Evap Cond Cond Disch Disch wt % Pres Pres PresPres Temp Ttemp Capacity Capacity Composition PEIK wt % B (Psia) (kPa)(Psia) (kPa) (F.) (C.) COP (Btu/min) (kW) CFC-113 2.7 19 12.8 88 156.369.1 4.18 14.8 0.26 PEIK plus B: HFOC-245caEαβ 47.6 52.4 3.4 24 17.1 118142.7 61.5 4.03 21.2 0.37 HFOC-245eaE 66.2 33.8 2.7 19 14.3 98 138.158.9 3.98 17.0 0.30 HFOC-245ebEβγ 52.4 47.6 3.9 27 18.9 130 139.7 59.83.99 23.4 0.41 HFOC-254cbEβγ 59.7 40.3 5.3 37 25.3 174 139.3 59.6 3.7929.6 0.52 HFOC-254ebEβγ 63.6 36.4 4.7 33 22.9 158 138.1 58.9 3.83 27.10.47 HFOC-254faE 73.3 26.7 3.8 26 18.8 130 135.1 57.3 3.88 22.2 0.39HFOC-263ebEβγ 79.4 20.6 3.8 26 19.4 134 134.9 57.2 3.83 22.4 0.39HFOC-272fbEβγ 75.3 24.7 4.4 30 21.7 150 138.9 59.4 3.83 25.5 0.45HFOC-347mccEγδ 39.5 60.5 4.7 32 21.7 150 130.8 54.9 3.82 25.8 0.45HFOC-347mfcEαβ 58.8 41.2 3.4 24 17.4 120 130.1 54.5 3.82 20.1 0.35HFOC-347mcfEβγ 57.8 42.2 3.6 25 17.9 123 130.2 54.6 3.81 20.6 0.36HFOC-347mcfEγδ 58.5 41.5 3.5 24 17.5 121 130.1 54.5 3.82 20.2 0.35 HFOC-78.0 22.0 2.6 18 13.9 96 128.1 53.4 3.79 15.6 0.27 347mmzEβγ HFOC- 78.621.4 2.2 15 12.5 86 128.5 53.6 3.82 13.9 0.24 356mecE2αβγδHFOC-356mecEγδ 73.7 26.3 3.3 23 17.0 117 128.7 53.7 3.75 19.2 0.34 HFOC-71.0 29.0 3.1 21 16.0 110 129.4 54.1 3.8 18.2 0.32 356mmzEβγHFOC-365mcEγδ 69.0 31.0 3.4 23 17.3 119 130.4 54.7 3.8 19.9 0.35HFOC-365mpzEβγ 70.3 29.7 2.8 19 14.8 102 131.6 55.3 3.87 17.1 0.30HFOC-374mefEβγ 79.6 20.4 3.0 21 15.8 109 129.7 54.3 3.81 18.0 0.32HFOC-374pcEβγ 74.8 25.2 3.2 22 16.6 114 130.7 54.8 3.82 19.0 0.33HFOC-383mEβγ 73.4 26.6 3.3 23 17.0 117 132.3 55.7 3.85 19.7 0.35HFOC-383mEγδ 78.3 21.7 3.3 23 17.0 117 130.9 54.9 3.81 19.4 0.34HFOC-383mzEβγ 72.4 27.6 3.8 26 18.9 130 13.24 −10.4 3.81 21.8 0.38HFOC-383peEβγ 76.0 24.0 3.8 26 19.5 134 132.4 55.8 3.78 22.2 0.39 HFOC-58.0 42.0 3.2 22 16.1 111 126.7 52.6 3.77 18.2 0.32 467mmyEβγHFOC-467mccEγδ 68.9 31.1 2.8 19 14.7 101 126.3 52.4 3.76 16.3 0.29HFOC-494pcEβγ 85.3 14.7 2.6 18 13.9 96 126.7 52.6 3.77 15.5 0.27 HFOC-78.8 21.2 3.0 21 15.6 108 129.7 54.3 3.81 17.8 0.31 C345mzeEαβ C₄F₉OCH₃77.0 23.0 2.5 18 13.7 95 125 51.7 3.73 15.0 0.26 C₄F₉OC₂H₅ 96.6 3.4 2.114 12.1 83 125 51.7 3.75 12.9 0.23 HFOC-356pccEγδ 80.6 19.4 2.8 19 14.9102 127.6 53.1 3.77 16.6 0.29 HFOC-356pcfEβγ 86.5 13.5 2.5 17 13.4 93127.3 52.9 3.78 14.9 0.26 HFOC-356pcfEγδ 83.4 16.6 2.5 17 13.4 93 127.853.2 3.8 15.0 0.26

Data show the compositions of the present invention have evaporator andcondenser pressures similar to CFC-113. Some compositions also havehigher capacity or energy efficiency (COP) than CFC-113.

1. An azeotropic composition comprising: 77.0 weight percent1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 23.0weight percent C₄F₉OCH₃ having a vapor pressure of about 14.7 psia (101kPa) at a temperature of about 45.2° C.
 2. A process for producingrefrigeration, said process comprising evaporating the composition ofclaim 1 in the vicinity of a body to be cooled, and thereaftercondensing said composition.
 3. A process for producing heat, saidprocess comprising condensing the composition of claim 1 in the vicinityof a body to be heated, and thereafter evaporating said composition. 4.A method for transferring heat, said method comprising transferring thecompositions of claim 1 from a heat source to a heat sink.
 5. Thecomposition of claim 1 further comprising at least one ultra-violetfluorescent dye selected from the group consisting of naphthalimides,perylenes, coumarins, anthracenes, phenanthracenes, xanthenes,thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dyeand combinations thereof.
 6. The composition of claim 5, furthercomprising at least one solubilizing agent selected from the groupconsisting of hydrocarbons, dimethylether, polyoxyalkylene glycolethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, arylethers, hydrofluoroethers, and 1,1,1-trifluoroalkanes; and wherein therefrigerant and solubilizing agent are not the same compound.
 7. Thecomposition of claim 6, wherein said solubilizing agent is selected fromthe group consisting of: a) polyoxyalkylene glycol ethers represented bythe formula R¹[(OR²)_(x)OR³]_(y), wherein: x is an integer from 1 to 3;y is an integer from 1 to 4; R¹ is selected from hydrogen and aliphatichydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R²is selected from aliphatic hydrocarbylene radicals having from 2 to 4carbon atoms; R³ is selected from hydrogen, and aliphatic and alicyclichydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R¹and R³ is selected from said hydrocarbon radicals; and wherein saidpolyoxyalkylene glycol ethers have a molecular weight of from about 100to about 300 atomic mass units; b) amides represented by the formulaeR¹C(O)NR²R³ and cyclo-[R⁴CON(R⁵)—], wherein R¹, R², R³ and R⁵ areindependently selected from aliphatic and alicyclic hydrocarbon radicalshaving from 1 to 12 carbon atoms, and at most one aromatic radicalhaving from 6 to 12 carbon atoms; R⁴ is selected from aliphatichydrocarbylene radicals having from 3 to 12 carbon atoms; and whereinsaid amides have a molecular weight of from about 100 to about 300atomic mass units; c) ketones represented by the formula R¹C(O)R²,wherein R¹ and R² are independently selected from aliphatic, alicyclicand aryl hydrocarbon radicals having from 1 to 12 carbon atoms, andwherein said ketones have a molecular weight of from about 70 to about300 atomic mass units; d) nitriles represented by the formula R¹CN,wherein R¹ is selected from aliphatic, alicyclic or aryl hydrocarbonradicals having from 5 to 12 carbon atoms, and wherein said nitrileshave a molecular weight of from about 90 to about 200 atomic mass units;e) chlorocarbons represented by the formula RCl_(x), wherein; x is 1 or2; R is selected from aliphatic and alicyclic hydrocarbon radicalshaving from 1 to 12 carbon atoms; and wherein said chlorocarbons have amolecular weight of from about 100 to about 200 atomic mass units; f)aryl ethers represented by the formula R¹OR², wherein: R¹ is selectedfrom aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R² isselected from aliphatic hydrocarbon radicals having from 1 to 4 carbonatoms; and wherein said aryl ethers have a molecular weight of fromabout 100 to about 150 atomic mass units; g) 1,1,1-trifluoroalkanesrepresented by the formula CF₃R¹, wherein R¹ is selected from aliphaticand alicyclic hydrocarbon radicals having from about 5 to about 15carbon atoms; i) fluoroethers represented by the formula R¹OCF₂CF₂H,wherein R¹ is selected from aliphatic and alicyclic hydrocarbon radicalshaving from about 5 to about 15 carbon atoms; or wherein saidfluoroethers are derived from fluoro-olefins and polyols, wherein saidfluoro-olefins are of the type CF₂═CXY, wherein X is hydrogen, chlorineor fluorine, and Y is chlorine, fluorine, CF₃ or OR_(f), wherein R_(f)is CF₃, C₂F₅, or C₃F₇; and said polyols are of the typeHOCH₂CRR′(CH₂)_(z)(CHOH)_(x)CH₂(CH₂OH)_(y), wherein R and R′ arehydrogen, CH₃ or C₂H₅, x is an integer from 0-4, y is an integer from0-3 and z is either zero or 1; and j) lactones represented by structures[B], [C], and [D]:

 wherein, R₁ through R₈ are independently selected from hydrogen,linear, branched, cyclic, bicyclic, saturated and unsaturatedhydrocarbyl radicals; and the molecular weight is from about 100 toabout 300 atomic mass units; and k) esters represented by the generalformula R¹CO₂R², wherein R¹ and R² are independently selected fromlinear and cyclic, saturated and unsaturated, alkyl and aryl radicals;and wherein said esters have a molecular weight of from about 80 toabout 550 atomic mass units.
 8. A method for detecting the compositionof claim 5 in a compression refrigeration or air conditioning apparatus,said method comprising providing said composition to said apparatus, andproviding a suitable means for detecting said composition at a leakpoint or in the vicinity of said apparatus.
 9. A method of producingrefrigeration, said method comprising: evaporating said composition ofclaim 5 in the vicinity of a body to be cooled and thereafter condensingsaid composition.
 10. A method of producing heat, said methodcomprising: condensing said composition of claim 5 in the vicinity ofthe body to be heated and thereafter evaporation said composition. 11.The composition of claim 1 further comprising a stabilizer, waterscavenger, or odor masking agent.
 12. The composition of claim 11wherein said stabilizer is selected from the group consisting ofnitromethane, hindered phenols, hydroxylamines, thiols, phosphites andlactones.
 13. A method of using the composition of claim 1 wherein saidmethod comprises producing heat or refrigeration in a refrigeration orair conditioning apparatus employing a multi-stage centrifugalcompressor.
 14. The method of claim 13 wherein said multi-stagecentrifugal compressor is a two-stage centrifugal compressor.
 15. Thecomposition of claim 11 wherein said water scavenger is an ortho ester.